U.S. Patent: 6071979 - Photoreactor composition method of generating a reactive species and applications therefor

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United States Patent	*6,071,979*
MacDonald , et al.	June 6, 2000

Photoreactor composition method of generating a reactive species and applications therefor

Abstract

A method of generating reactive species which includes exposing a wavelength specific photoreactor to radiation, in which the wavelength specific photoreactor comprises a wavelength-specific sensitizer associated with one or more reactive species-generating photoinitiators. Also described are methods of polymerizing unsaturated monomers and curing an unsaturated oligomer/monomer mixture.

Inventors:	MacDonald; John Gavin (Decatur, GA); Nohr; Ronald Sinclair (Alpharetta, GA)
Assignee:	Kimberly-Clark Worldwide, Inc. (Neenah, WI)
Appl. No.:	998464
Filed:	December 26, 1997

Current U.S. Class: 522/34; 428/378; 442/59; 442/152; 442/164; 442/172; 522/33; 522/36; 522/39; 522/40; 522/42; 522/71; 522/81

Intern'l Class: C08F 002/50; C08J 003/28

Field of Search: 522/8,9,14,16,19,34,36,39,42,40,71,81 428/378 442/59,152,164,172

References Cited U.S. Patent Documents

Re28225	Nov., 1974	Heseltine et al.
Re28789	Apr., 1976	Chang.
575228	Jan., 1897	Von Gallois.
582853	May., 1897	Feer.
893636	Jul., 1908	Maywald.
1013544	Jan., 1912	Fuerth.
1325971	Dec., 1919	Akashi.
1364406	Jan., 1921	Olsen.
1436856	Nov., 1922	Brenizer et al.
1744149	Jan., 1930	Staehlin.
1803906	May., 1931	Krieger et al.
1844199	Feb., 1932	Bicknell et al.
1876880	Sep., 1932	Drapal.
1880572	Oct., 1932	Wendt et al.
1880573	Oct., 1932	Wendt et al.
1916350	Jul., 1933	Wendt et al.
1916779	Jul., 1933	Wendt et al.
1955898	Apr., 1934	Wendt et al.
1962111	Jun., 1934	Bamberger.
2005378	Jun., 1935	Kiel.
2005511	Jun., 1935	Stoll et al.
2049005	Jul., 1936	Gaspar.
2054390	Sep., 1936	Rust et al.
2058489	Oct., 1936	Murch et al.
2062304	Dec., 1936	Gaspar.
2090511	Aug., 1937	Crossley et al.
2097119	Oct., 1937	Eggert.
2106539	Jan., 1938	Schnitzspahn.
2111692	Mar., 1938	Saunders et al.
2125015	Jul., 1938	Gaspar.
2130572	Sep., 1938	Wendt.
2132154	Oct., 1938	Gaspar.
2145960	Feb., 1939	Wheatley et al.
2154996	Apr., 1939	Rawling.
2159280	May., 1939	Mannes et al.
2171976	Sep., 1939	Erickson.
2181800	Nov., 1939	Crossley et al.
2185153	Dec., 1939	Lecher et al.
2220178	Nov., 1940	Schneider.
2230590	Feb., 1941	Eggert et al.
2237885	Apr., 1941	Markush et al.
2243630	May., 1941	Houk et al.
2268324	Dec., 1941	Polgar.
2281895	May., 1942	van Poser et al.
2328166	Aug., 1943	Poigar et al.
2346090	Apr., 1944	Staehle.
2349090	May., 1944	Haddock.
2356618	Aug., 1944	Rossander et al.
2361301	Oct., 1944	Libby, Jr. et al.
2364359	Dec., 1944	Kienle et al.
2381145	Aug., 1945	von Glahn et al.
2382904	Aug., 1945	Federsen.
2386646	Oct., 1945	Adams et al.
2402106	Jun., 1946	von Glahn et al.
2416145	Feb., 1947	Biro.
2477165	Jul., 1949	Bergstrom.
2527347	Oct., 1950	Bergstrom.
2580461	Jan., 1952	Pearl.
2601669	Jun., 1952	Tullsen.
2612494	Sep., 1952	Von Glahn et al..
2612495	Sep., 1952	Von Glahn et al.
2628959	Feb., 1953	Von Glahn et al.
2647080	Jul., 1953	Joyce.
2680685	Jun., 1954	Ratchford.
2728784	Dec., 1955	Tholstrup et al.
2732301	Jan., 1956	Robertson et al.
2744103	May., 1956	Koch.
2757090	Jul., 1956	Meugebauer et al.
2763550	Sep., 1956	Lovick.
2768171	Oct., 1956	Clarke et al.
2773056	Dec., 1956	Helfaer.
2798000	Jul., 1957	Monterman.
2809189	Oct., 1957	Stanley et al.
2827358	Mar., 1958	Kaplan et al.
2834773	May., 1958	Scalera et al.
2875045	Feb., 1959	Lurie.
2892865	Jun., 1959	Giraldi et al.
2897187	Jul., 1959	Koch.
2936241	May., 1960	Sharp et al.
2940853	Jun., 1960	Sagura et al.
2955067	Oct., 1960	McBurney et al.
2992129	Jul., 1961	Gauthier.
2992198	Jul., 1961	Funahashi.
3030208	Apr., 1962	Schellenberg et al.
3071815	Jan., 1963	MacKinnon.
3075014	Jan., 1963	Palopoli et al.
3076813	Feb., 1963	Sharp.
3104973	Sep., 1963	Sprague et al.
3114634	Dec., 1963	Brown et al.
3121632	Feb., 1964	Sprague et al.
3123647	Mar., 1964	Duennenberger et al.
3133049	May., 1964	Hertel et al.
3140949	Jul., 1964	Sprague et al.
3154416	Oct., 1964	Fidelman.
3155509	Nov., 1964	Roscow.
3175905	Mar., 1965	Wiesbaden.
3178285	Apr., 1965	Anderau et al.
3238163	Mar., 1966	O'Neill.
3242215	Mar., 1966	Heitmiller.
3248337	Apr., 1966	Zirker et al.
3266973	Aug., 1966	Crowley.
3282886	Nov., 1966	Gadecki.
3284205	Nov., 1966	Sprague et al.
3300314	Jan., 1967	Rauner et al.
3304297	Feb., 1967	Wegmann et al.
3305361	Feb., 1967	Gaynor et al.
3313797	Apr., 1967	Kissa.
3330659	Jul., 1967	Wainer.
3341492	Sep., 1967	Champ et al.
3359109	Dec., 1967	Harder et al.
3361827	Jan., 1968	Biletch.
3363969	Jan., 1968	Brooks.
3385700	May., 1968	Willems et al.
3397984	Aug., 1968	Williams et al.
3415875	Dec., 1968	Luethi et al.
3418118	Dec., 1968	Thommes et al.
3445234	May., 1969	Cescon et al.
3453258	Jul., 1969	Parmerter et al.
3453259	Jul., 1969	Parmerter et al.
3464841	Sep., 1969	Skofronick.
3479185	Nov., 1969	Chambers.
3502476	Mar., 1970	Kohei et al.
3503744	Mar., 1970	Itano et al.
3514597	May., 1970	Haes et al.
3541142	Nov., 1970	Cragoe, Jr.
3546161	Dec., 1970	Wolheim.
3547646	Dec., 1970	Hori et al.
3549367	Dec., 1970	Chang et al.
3553710	Jan., 1971	Lloyd et al.
3563931	Feb., 1971	Horiguchi.
3565753	Feb., 1971	Yurkowitz.
3574624	Apr., 1971	Reynolds et al.
3579533	May., 1971	Yalman.
3595655	Jul., 1971	Robinson et al.
3595657	Jul., 1971	Robinson et al.
3595658	Jul., 1971	Gerlach et al.
3595659	Jul., 1971	Gerlach et al.
3607639	Sep., 1971	Krefeld et al.
3607693	Sep., 1971	Heine et al.
3607863	Sep., 1971	Dosch.
3615562	Oct., 1971	Harrison et al.
3617288	Nov., 1971	Hartman et al.
3617335	Nov., 1971	Kumura et al.
3619238	Nov., 1971	Kimura et al.
3619239	Nov., 1971	Osada et al.
3637337	Jan., 1972	Pilling.
3637581	Jan., 1972	Horioguchi et al.
3642472	Feb., 1972	Mayo.
3647467	Mar., 1972	Grubb.
3652275	Mar., 1972	Baum et al.
3660542	May., 1972	Adachi et al.
3667954	Jun., 1972	Itano et al.
3668188	Jun., 1972	King et al.
3669925	Jun., 1972	King et al.
3671096	Jun., 1972	Mackin.
3671251	Jun., 1972	Houle et al.
3676690	Jul., 1972	McMillin et al.
3678044	Jul., 1972	Adams.
3689565	Sep., 1972	Hoffmann et al.
3694241	Sep., 1972	Guthrie et al.
3695879	Oct., 1972	Laming et al.
3697280	Oct., 1972	Strilko.
3705043	Dec., 1972	Zablak.
3707371	Dec., 1972	Files.
3729313	Apr., 1973	Smith.
3737628	Jun., 1973	Azure.
3765896	Oct., 1973	Fox.
3775130	Nov., 1973	Enomoto et al.
3788849	Jan., 1974	Taguchi et al.
3799773	Mar., 1974	Watarai et al.
3800439	Apr., 1974	Sokolski et al.
3801329	Apr., 1974	Sandner et al.
3817752	Jun., 1974	Laridon et al.
3840338	Oct., 1974	Zviak et al.
3844790	Oct., 1974	Chang et al.
3870524	Mar., 1975	Watanabe et al.
3873500	Mar., 1975	Kato et al.
3876496	Apr., 1975	Lozano.
3887450	Jun., 1975	Gilano et al.
3895949	Jul., 1975	Akamatsu.
3901779	Aug., 1975	Mani.
3910993	Oct., 1975	Avar et al.
3914165	Oct., 1975	Gaske.
3914166	Oct., 1975	Rudolph et al.
3915824	Oct., 1975	McGinniss.
3919323	Nov., 1975	Houlihan et al.
3926641	Dec., 1975	Rosen.
3928264	Dec., 1975	Young, Jr. et al.
3933682	Jan., 1976	Bean.
3952129	Apr., 1976	Matsukawa et al.
3960685	Jun., 1976	Sano et al.
3965157	Jun., 1976	Harrison.
3978132	Aug., 1976	Houlihan et al.
3984248	Oct., 1976	Sturmer.
3988154	Oct., 1976	Sturmer.
4004998	Jan., 1977	Rosen.
4012256	Mar., 1977	Levinos.
4017652	Apr., 1977	Gruber.
4022674	May., 1977	Rosen.
4024324	May., 1977	Sparks.
4039332	Aug., 1977	Kokelenberg et al.
4043819	Aug., 1977	Baumann.
4048034	Sep., 1977	Martan.
4054719	Oct., 1977	Cordes, III.
4056665	Nov., 1977	Tayler et al.
4058400	Nov., 1977	Crivello.
4067892	Jan., 1978	Thorne et al.
4071424	Jan., 1978	Dart et al.
4073968	Feb., 1978	Miyamoto et al.
4077769	Mar., 1978	Garcia.
4079183	Mar., 1978	Green.
4085062	Apr., 1978	Virgilio et al.
4090877	May., 1978	Streeper.
4100047	Jul., 1978	McCarty.
4105572	Aug., 1978	Gorondy.
4107733	Aug., 1978	Schickedanz.
4110112	Aug., 1978	Roman et al.
4111699	Sep., 1978	Krueger.
4114028	Sep., 1978	Baio et al.
4126412	Nov., 1978	Masson et al.
4141807	Feb., 1979	Via.
4144156	Mar., 1979	Kuesters et al.
4148658	Apr., 1979	Kondoh et al.
4162162	Jul., 1979	Dueber.
4171977	Oct., 1979	Hasegawa et al.
4179577	Dec., 1979	Green.
4181807	Jan., 1980	Green.
4190671	Feb., 1980	Vanstone et al.
4197080	Apr., 1980	Mee.
4199420	Apr., 1980	Photis.
4229172	Oct., 1980	Baumann et al.
4232106	Nov., 1980	Iwasaki et al.
4238492	Dec., 1980	Majoie.
4239843	Dec., 1980	Hara et al.
4239850	Dec., 1980	Kita et al.
4241155	Dec., 1980	Hara et al.
4242430	Dec., 1980	Hara et al.
4242431	Dec., 1980	Hara et al.
4245018	Jan., 1981	Hara et al.
4245995	Jan., 1981	Hugl et al.
4246330	Jan., 1981	Hara et al.
4248949	Feb., 1981	Hara et al.
4250096	Feb., 1981	Kvita et al.
4251622	Feb., 1981	Kimoto et al.
4254195	May., 1981	Nakamura.
4256493	Mar., 1981	Yokoyama et al.
4256817	Mar., 1981	Hara et al.
4258123	Mar., 1981	Nagashima et al.
4258367	Mar., 1981	Mansukhani.
4259432	Mar., 1981	Kondoh et al.
4262936	Apr., 1981	Miyamoto.
4268605	May., 1981	Hara et al.
4268667	May., 1981	Anderson.
4269926	May., 1981	Hara et al.
4270130	May., 1981	Houle et al.
4271252	Jun., 1981	Hara et al.
4271253	Jun., 1981	Hara et al.
4272244	Jun., 1981	Schlick.
4276211	Jun., 1981	Singer et al.
4277497	Jul., 1981	Fromantin.
4279653	Jul., 1981	Makishima et al.
4279982	Jul., 1981	Iwasaki et al.
4279985	Jul., 1981	Nonogaki et al.
4284485	Aug., 1981	Berner.
4288631	Sep., 1981	Ching.
4289844	Sep., 1981	Specht et al.
4290870	Sep., 1981	Kondoh et al.
4293458	Oct., 1981	Gruenberger et al.
4298679	Nov., 1981	Shinozaki et al.
4300123	Nov., 1981	McMillin et al.
4301223	Nov., 1981	Nakamura et al.
4302606	Nov., 1981	Barabas et al.
4306014	Dec., 1981	Kunikane et al.
4307182	Dec., 1981	Dalzell et al.
4308400	Dec., 1981	Felder et al.
4315807	Feb., 1982	Felder et al.
4318705	Mar., 1982	Nowak et al.
4318791	Mar., 1982	Felder et al.
4321118	Mar., 1982	Felder et al.
4335054	Jun., 1982	Blaser et al.
4335055	Jun., 1982	Blaser et al.
4336323	Jun., 1982	Winslow.
4343891	Aug., 1982	Aasen et al.
4345011	Aug., 1982	Drexhage.
4347111	Aug., 1982	Gehlhaus et al.
4349617	Sep., 1982	Kawashiri et al.
4350753	Sep., 1982	Shelnut et al.
4351893	Sep., 1982	Anderson.
4356255	Oct., 1982	Tachikawa et al.
4357468	Nov., 1982	Szejtli et al.
4359524	Nov., 1982	Masuda et al.
4362806	Dec., 1982	Whitmore.
4367072	Jan., 1983	Vogtle et al.
4367280	Jan., 1983	Kondo et al.
4369283	Jan., 1983	Altschuler.
4370401	Jan., 1983	Winslow et al.
4372582	Feb., 1983	Geisler.
4373017	Feb., 1983	Masukawa et al.
4373020	Feb., 1983	Winslow.
4374984	Feb., 1983	Eichler et al.
4376887	Mar., 1983	Greenaway et al.
4383835	May., 1983	Preuss et al.
4390616	Jun., 1983	Sato et al.
4391867	Jul., 1983	Derick et al.
4399209	Aug., 1983	Sanders et al.
4400173	Aug., 1983	Beavan.
4401470	Aug., 1983	Bridger.
4416961	Nov., 1983	Drexhage.
4421559	Dec., 1983	Owatari.
4424325	Jan., 1984	Tsunoda et al.
4425162	Jan., 1984	Sugiyama.
4425424	Jan., 1984	Altland et al.
4426153	Jan., 1984	Libby et al.
4434035	Feb., 1984	Eichler et al.
4447521	May., 1984	Tiers et al.
4450227	May., 1984	Holmes et al.
4460676	Jul., 1984	Fabel.
4467112	Aug., 1984	Matsuura et al.
4475999	Oct., 1984	Via.
4477681	Oct., 1984	Gehlhaus et al.
4489334	Dec., 1984	Owatari.
4495041	Jan., 1985	Goldstein.
4496447	Jan., 1985	Eichler et al.
4500355	Feb., 1985	Shimada et al.
4508570	Apr., 1985	Fugii et al.
4510392	Apr., 1985	Litt et al.
4523924	Jun., 1985	Lacroix.
4524122	Jun., 1985	Weber et al.
4534838	Aug., 1985	Lin et al.
4548896	Oct., 1985	Sabongi et al.
4555474	Nov., 1985	Kawamura.
4557730	Dec., 1985	Bennett et al.
4565769	Jan., 1986	Dueber et al.
4567171	Jan., 1986	Mangum.
4571377	Feb., 1986	McGinniss et al.
4595745	Jun., 1986	Nakano et al.
4604344	Aug., 1986	Irving et al.
4605442	Aug., 1986	Kawashita et al.
4613334	Sep., 1986	Thomas et al.
4614723	Sep., 1986	Schmidt et al.
4617380	Oct., 1986	Hinson et al.
4620875	Nov., 1986	Shimada et al.
4620876	Nov., 1986	Fugii et al.
4622286	Nov., 1986	Sheets.
4631085	Dec., 1986	Kawanishi et al.
4632891	Dec., 1986	Banks et al.
4632895	Dec., 1986	Patel et al.
4634644	Jan., 1987	Irving et al.
4638340	Jan., 1987	Iiyama et al.
4647310	Mar., 1987	Shimada et al.
4655783	Apr., 1987	Reinert et al.
4663275	May., 1987	West et al.
4663641	May., 1987	Iiyama et al.
4668533	May., 1987	Miller.
4672041	Jun., 1987	Jain.
4698291	Oct., 1987	Koibuchi et al.
4701402	Oct., 1987	Patel et al.
4702996	Oct., 1987	Griffing et al.
4704133	Nov., 1987	Reinert et al.
4707161	Nov., 1987	Thomas et al.
4707425	Nov., 1987	Sasagawa et al.
4707430	Nov., 1987	Ozawa et al.
4711668	Dec., 1987	Shimada et al.
4711802	Dec., 1987	Tannenbaum.
4713113	Dec., 1987	Shimada et al.
4720450	Jan., 1988	Ellis.
4721531	Jan., 1988	Wildeman et al.
4721734	Jan., 1988	Gehlhaus et al.
4724021	Feb., 1988	Martin et al.
4724201	Feb., 1988	Okazaki et al.
4725527	Feb., 1988	Robillard.
4727824	Mar., 1988	Ducharme et al.
4732615	Mar., 1988	Kawashita et al.
4737190	Apr., 1988	Shimada et al.
4737438	Apr., 1988	Ito et al.
4740451	Apr., 1988	Kohara.
4745042	May., 1988	Sasago et al.
4746735	May., 1988	Kruper, Jr. et al.
4752341	Jun., 1988	Rock.
4755450	Jul., 1988	Sanders et al.
4761181	Aug., 1988	Suzuki.
4766050	Aug., 1988	Jerry.
4766055	Aug., 1988	Kawabata et al.
4770667	Sep., 1988	Evans et al.
4772291	Sep., 1988	Shibanai et al.
4772541	Sep., 1988	Gottschalk.
4775386	Oct., 1988	Reinert et al.
4786586	Nov., 1988	Lee et al.
4789382	Dec., 1988	Neumann et al.
4790565	Dec., 1988	Steed.
4800149	Jan., 1989	Gottschalk.
4803008	Feb., 1989	Ciolino et al.
4808189	Feb., 1989	Oishi et al.
4812139	Mar., 1989	Brodmann.
4812517	Mar., 1989	West.
4813970	Mar., 1989	Kirjanov et al.
4822714	Apr., 1989	Sanders.
4831068	May., 1989	Reinert et al.
4834771	May., 1989	Yamauchi et al.
4837106	Jun., 1989	Ishikawa et al.
4837331	Jun., 1989	Yamanishi et al.
4838938	Jun., 1989	Tomida et al.
4839269	Jun., 1989	Okazaki et al.
4849320	Jul., 1989	Irving et al.
4853037	Aug., 1989	Johnson et al.
4853398	Aug., 1989	Carr et al.
4854971	Aug., 1989	Gane et al.
4857438	Aug., 1989	Loerzer et al.
4861916	Aug., 1989	Kohler et al.
4865942	Sep., 1989	Gottschalk et al.
4874391	Oct., 1989	Reinert.
4874899	Oct., 1989	Hoelderich et al.
4885395	Dec., 1989	Hoelderich.
4886774	Dec., 1989	Doi.
4892941	Jan., 1990	Dolphin et al.
4895880	Jan., 1990	Gottschalk.
4900581	Feb., 1990	Stuke et al.
4902299	Feb., 1990	Anton.
4902725	Feb., 1990	Moore.
4902787	Feb., 1990	Freeman.
4911732	Mar., 1990	Neumann et al.
4911899	Mar., 1990	Hagiwara et al.
4917956	Apr., 1990	Rohrbach.
4921317	May., 1990	Suzuki et al.
4925770	May., 1990	Ichiura et al.
4925777	May., 1990	Inoue et al.
4926190	May., 1990	Lavar.
4933265	Jun., 1990	Inoue et al.
4933948	Jun., 1990	Herkstroeter.
4937161	Jun., 1990	Kita et al.
4942113	Jul., 1990	Trundle.
4950304	Aug., 1990	Reinert et al.
4952478	Aug., 1990	Miyagawa et al.
4952680	Aug., 1990	Schmeidl.
4954380	Sep., 1990	Kanome et al.
4954416	Sep., 1990	Wright et al.
4956254	Sep., 1990	Washizu et al.
4964871	Oct., 1990	Reinert et al.
4965294	Oct., 1990	Ohngemach et al.
4966607	Oct., 1990	Shinoki et al.
4966833	Oct., 1990	Inoue.
4968596	Nov., 1990	Inoue et al.
4968813	Nov., 1990	Rule et al.
4985345	Jan., 1991	Hayakawa et al.
4987056	Jan., 1991	Imahashi et al.
4988561	Jan., 1991	Wason.
4997745	Mar., 1991	Kawamura et al.
5001330	Mar., 1991	Koch.
5002853	Mar., 1991	Aoai et al.
5002993	Mar., 1991	West et al.
5003142	Mar., 1991	Fuller.
5006758	Apr., 1991	Gellert et al.
5013959	May., 1991	Kogelschatz.
5017195	May., 1991	Satou et al.
5023129	Jun., 1991	Morganti et al.
5025036	Jun., 1991	Carson et al.
5026425	Jun., 1991	Hindagolla et al.
5026427	Jun., 1991	Mitchell et al.
5028262	Jul., 1991	Barlow, Jr. et al.
5028792	Jul., 1991	Mullis.
5030243	Jul., 1991	Reinert.
5030248	Jul., 1991	Meszaros.
5034526	Jul., 1991	Bonham et al.
5037726	Aug., 1991	Kojima et al.
5045435	Sep., 1991	Adams et al.
5045573	Sep., 1991	Kohler et al.
5047556	Sep., 1991	Kohler et al.
5049777	Sep., 1991	Mechtersheimer.
5053320	Oct., 1991	Robbillard.
5055579	Oct., 1991	Pawlowski et al.
5057562	Oct., 1991	Reinert.
5068364	Nov., 1991	Takagaki et al.
5069681	Dec., 1991	Bouwknegt et al.
5070001	Dec., 1991	Stahlhofen.
5073448	Dec., 1991	Vieira et al.
5074885	Dec., 1991	Reinert.
5076808	Dec., 1991	Hahn et al.
5085698	Feb., 1992	Ma et al.
5087550	Feb., 1992	Blum et al.
5089050	Feb., 1992	Vieira et al.
5089374	Feb., 1992	Saeva.
5096456	Mar., 1992	Reinert et al.
5096489	Mar., 1992	Laver.
5096781	Mar., 1992	Vieira et al.
5098477	Mar., 1992	Vieira et al.
5098793	Mar., 1992	Rohrbach et al.
5098806	Mar., 1992	Robillard.
5106723	Apr., 1992	West et al.
5108505	Apr., 1992	Moffat.
5108874	Apr., 1992	Griffing et al.
5110706	May., 1992	Yumoto et al.
5110709	May., 1992	Aoai et al.
5114832	May., 1992	Zertani et al.
5124723	Jun., 1992	Laver.
5130227	Jul., 1992	Wade et al.
5133803	Jul., 1992	Moffatt.
5135940	Aug., 1992	Belander et al.
5139572	Aug., 1992	Kawashima.
5139687	Aug., 1992	Borgher, Sr. et al.
5141556	Aug., 1992	Matrick.
5141797	Aug., 1992	Wheeler.
5144964	Sep., 1992	Demain.
5147901	Sep., 1992	Rutsch et al.
5153104	Oct., 1992	Rossman et al.
5153105	Oct., 1992	Sher et al.
5153166	Oct., 1992	Jain et al.
5160346	Nov., 1992	Fuso et al.
5160372	Nov., 1992	Matrick.
5166041	Nov., 1992	Murofushi et al.
5169436	Dec., 1992	Matrick.
5169438	Dec., 1992	Matrick.
5173112	Dec., 1992	Matrick et al.
5176984	Jan., 1993	Hipps, Sr. et al.
5178420	Jan., 1993	Shelby.
5180425	Jan., 1993	Matrick et al.
5180652	Jan., 1993	Yamaguchi et al.
5181935	Jan., 1993	Reinert et al.
5185236	Feb., 1993	Shiba et al.
5187045	Feb., 1993	Bonham et al.
5187049	Feb., 1993	Sher et al.
5190565	Mar., 1993	Berenbaum et al.
5190710	Mar., 1993	Kletecka.
5190845	Mar., 1993	Hashimoto et al.
5193854	Mar., 1993	Borowski, Jr. et al.
5196295	Mar., 1993	Davis.
5197991	Mar., 1993	Rembold.
5198330	Mar., 1993	Martic et al.
5202209	Apr., 1993	Winnik et al.
5202210	Apr., 1993	Matsuoka et al.
5202211	Apr., 1993	Vercoulen.
5202212	Apr., 1993	Shin et al.
5202213	Apr., 1993	Nakahara et al.
5202215	Apr., 1993	Kanakura et al.
5202221	Apr., 1993	Imai et al.
5205861	Apr., 1993	Matrick.
5208136	May., 1993	Zanoni et al.
5209814	May., 1993	Felten et al.
5219703	Jun., 1993	Bugner et al.
5221334	Jun., 1993	Ma et al.
5224197	Jun., 1993	Zanoni et al.
5224987	Jul., 1993	Matrick.
5226957	Jul., 1993	Wickramanayake et al.
5227022	Jul., 1993	Leonhardt et al.
5241059	Aug., 1993	Yoshinaga.
5244476	Sep., 1993	Schulz et al.
5250109	Oct., 1993	Chan et al.
5254429	Oct., 1993	Gracia et al.
5256193	Oct., 1993	Winnik et al.
5258274	Nov., 1993	Helland et al.
5261953	Nov., 1993	Vieira et al.
5262276	Nov., 1993	Kawamura.
5268027	Dec., 1993	Chan et al.
5270078	Dec., 1993	Walker et al.
5271764	Dec., 1993	Winnik et al.
5271765	Dec., 1993	Ma.
5272201	Dec., 1993	Ma et al.
5275646	Jan., 1994	Marshall et al.
5279652	Jan., 1994	Kaufmann et al.
5282894	Feb., 1994	Albert et al.
5284734	Feb., 1994	Blum et al.
5286286	Feb., 1994	Winnik et al.
5286288	Feb., 1994	Tobias et al.
5294528	Mar., 1994	Furutachi.
5296275	Mar., 1994	Goman et al.
5296556	Mar., 1994	Frihart.
5298030	Mar., 1994	Burdeska et al.
5300403	Apr., 1994	Angelopolus et al.
5300654	Apr., 1994	Nakajima et al.
5302195	Apr., 1994	Helbrecht.
5302197	Apr., 1994	Wickramanayke et al.
5310778	May., 1994	Shor et al.
5312713	May., 1994	Yokoyama et al.
5312721	May., 1994	Gesign.
5324349	Jun., 1994	Sano et al.
5328504	Jul., 1994	Ohnishi.
5330860	Jul., 1994	Grot et al.
5334455	Aug., 1994	Noren et al.
5338319	Aug., 1994	Kaschig et al.
5340631	Aug., 1994	Matsuzawa et al.
5340854	Aug., 1994	Martic et al.
5344483	Sep., 1994	Hinton.
5356464	Oct., 1994	Hickman et al.
5362592	Nov., 1994	Murofushi et al.
5368689	Nov., 1994	Agnemo.
5372387	Dec., 1994	Wajda.
5372917	Dec., 1994	Tsuchida et al.
5374335	Dec., 1994	Lindgren et al.
5376503	Dec., 1994	Audett et al.
5383961	Jan., 1995	Bauer et al.
5384186	Jan., 1995	Trinh.
5393580	Feb., 1995	Ma et al.
5401303	Mar., 1995	Stoffel et al.
5401562	Mar., 1995	Akao.
5415686	May., 1995	Kurabayashi et al.
5415976	May., 1995	Ali.
5424407	Jun., 1995	Tanaka et al.
5425978	Jun., 1995	Berneth et al.
5426164	Jun., 1995	Babb et al.
5427415	Jun., 1995	Chang.
5429628	Jul., 1995	Trinh et al.
5431720	Jul., 1995	Nagai et al.
5432274	Jul., 1995	Luong et al.
5445651	Aug., 1995	Thoen et al.
5445842	Aug., 1995	Tanaka et al.
5455143	Oct., 1995	Ali.
5459014	Oct., 1995	Nishijima et al.
5464472	Nov., 1995	Horn et al.
5466283	Nov., 1995	Kondo et al.
5474691	Dec., 1995	Severns.
5475080	Dec., 1995	Gruber et al.
5476540	Dec., 1995	Shields et al.
5479949	Jan., 1996	Battard et al.
5489503	Feb., 1996	Toan.
5498345	Mar., 1996	Jollenbeck et al.
5501774	Mar., 1996	Burke.
5503664	Apr., 1996	Sano et al.
5509957	Apr., 1996	Toan et al.
5531821	Jul., 1996	Wu.
5532112	Jul., 1996	Kohler et al.
5541633	Jul., 1996	Winnik et al.
5543459	Aug., 1996	Hartmann et al.
5571313	Nov., 1996	Mafune et al.
5575891	Nov., 1996	Trokhan et al.
5580369	Dec., 1996	Belding et al.
5607803	Mar., 1997	Murofushi et al.
5643356	Jul., 1997	Nohr et al.	106/31.
5645964	Jul., 1997	Nohr et al.	430/21.
5685754	Nov., 1997	Nohr et al.	442/49.
5686503	Nov., 1997	Nohr et al.	522/36.
5709955	Jan., 1998	Nohr et al.	428/507.
5739175	Apr., 1998	Nohr et al.	522/34.
5747550	May., 1998	Nohr et al.	522/34.
5798015	Aug., 1998	Nohr et al.	156/275.
5811199	Sep., 1998	MacDonald et al.	428/515.
Foreign Patent Documents
103085	Apr., 1937	AU.
12624/88	Sep., 1988	AU.
413257	Oct., 1932	CA.
458808	Dec., 1936	CA.
460268	Oct., 1949	CA.
461082	Nov., 1949	CA.
463021	Feb., 1950	CA.
463022	Feb., 1950	CA.
465496	May., 1950	CA.
465495	May., 1950	CA.
465499	May., 1950	CA.
483214	May., 1952	CA.
517364	Oct., 1955	CA.
537687	Mar., 1957	CA.
552565	Feb., 1958	CA.
779239	Feb., 1968	CA.
930103	Jul., 1973	CA.
2053094	Apr., 1992	CA.
94118	May., 1958	CS.
0003884	Sep., 1979	EP.
0029284	May., 1981	EP.
0223587	May., 1987	EP.
0280458	Aug., 1988	EP.
0308274	Mar., 1989	EP.
0375160	Jun., 1990	EP.
0373662	Jun., 1990	EP.
0390439	Oct., 1990	EP.
0468465	Jan., 1992	EP.
0542286	May., 1993	EP.
000571190	Nov., 1993	EP.
0608433	Aug., 1994	EP.
0639664	Feb., 1995	EP.
1039835	Sep., 1958	DE.
1047013	Dec., 1958	DE.
1132450	Jul., 1962	DE.
2437380	Feb., 1975	DE.
2444520	Mar., 1975	DE.
2714978	Oct., 1977	DE.
3833438	Apr., 1990	DE.
3833437	Apr., 1990	DE.
004036328	Jul., 1991	DE.
5065592	Jun., 1975	JP.
5614569	Feb., 1981	JP.
0014233	Feb., 1981	JP.
56-36556	Apr., 1981	JP.
57128283	Aug., 1982	JP.
59-219270	Apr., 1985	JP.
60239740	Nov., 1985	JP.
60239743	Nov., 1985	JP.
60239739	Nov., 1985	JP.
60239741	Nov., 1985	JP.
613781	Jan., 1986	JP.
627703	Jan., 1987	JP.
62-100557	May., 1987	JP.
62127281	Jun., 1987	JP.
63-43959	Feb., 1988	JP.
63-223077	Sep., 1988	JP.
63-223078	Sep., 1988	JP.
6429337	Jan., 1989	JP.
64-40948	Feb., 1989	JP.
89014948	Mar., 1989	JP.
1146974	Jun., 1989	JP.
01210477	Aug., 1989	JP.
292957	Apr., 1990	JP.
2179642	Jul., 1990	JP.
2282261	Nov., 1990	JP.
03163566	Jul., 1991	JP.
5134447	Nov., 1991	JP.
3284668	Dec., 1991	JP.
4023885	Jan., 1992	JP.
4023884	Jan., 1992	JP.
4-136075	May., 1992	JP.
561220	Mar., 1993	JP.
5-140498	Jun., 1993	JP.
5263067	Oct., 1993	JP.
6116556	Apr., 1994	JP.
6116557	Apr., 1994	JP.
6116555	Apr., 1994	JP.
6214339	Aug., 1994	JP.
6256633	Sep., 1994	JP.
6256494	Sep., 1994	JP.
1310767	May., 1987	RU.
275245	Oct., 1928	GB.
349339	May., 1931	GB.
355686	Aug., 1931	GB.
399753	Oct., 1933	GB.
441085	Jan., 1936	GB.
463515	Apr., 1937	GB.
492711	Sep., 1938	GB.
518612	Mar., 1940	GB.
539912	Sep., 1941	GB.
626727	Jul., 1947	GB.
600451	Apr., 1948	GB.
616362	Jan., 1949	GB.
618616	Feb., 1949	GB.
779389	Jul., 1957	GB.
1372884	Nov., 1974	GB.
2146357	Apr., 1985	GB.
92/11295	Jul., 1992	WO.
93/06597	Apr., 1993	WO.
94/01503	Jan., 1994	WO.
94/22501	Oct., 1994	WO.
94/22500	Oct., 1994	WO.
95/04955	Feb., 1995	WO.
96/00740	Jan., 1996	WO.
96/19502	Jun., 1996	WO.
96/22335	Jul., 1996	WO.

Other References

Kubat et al. "Photophysical properties of metal complexes of meso-tetrakis (40sulphonatophenyl) porphyrin," J. Photochem. and Photobiol. 96 93-97 1996.
Abstract for WO 95/00343--A1 Textiles: Paper: Cellulose p. 7 1995.
Maki, Y. et al. "A novel heterocyclic N-oxide, pyrimido[5,4-g]pteridinetetrone 5-oxide, with multifunctional photooxidative properties" Chemical Abstracts 122 925 [no 122:31350 F] 1995.
Abstract of patent, JP 6-80915 (Canon Inc.), Mar. 22, 1994.
Abstract of patent, JP 06-43573 (Iku Meji) (Feb. 18, 1994).
Pitchumani, K. et al. "Modification of chemical reactivity upon cyclodextrin encapsulation" Chemical Abstracts 121 982 [No. 121:13362 4v] 1994.
Derwent Publications Ltd., London, JP 05297627 (Fujitsu Ltd.), Nov. 12, 1993. (Abstract).
Patent Abstracts of Japan, JP 5241369 (Bando Chem Ind Ltd et al.), Sep. 21, 1993. (Abstract).
Derwent Publications Ltd., London, JP 05232738 (Yamazaki, T.), Sep. 10, 1993. (Abstract).
Derwent Publications Ltd., London, EP 000559310 (Zeneca Ltd.), Sep. 8, 1993. (Abstract).
Derwent Publications Ltd., London, J,A, 5-230410 (Seiko Epson Corp), Sep. 7, 1993. (Abstract).
Derwent Publications Ltd., London, JP 5-230407 (Mitsubishi Kasei Corp), Sep. 7, 1993. (Abstract).
Abstract Of Patent, JP 405230410 (Seiko Epson Corp.), Sep. 7, 1993. (Abstract).
Abstract Of Patent, JP 405230407 (Mitsubishi Kasei Corp.), Sep. 7, 1993. (Abstract).
Patent Abstracts of Japan, JP 5197198 (Bando Chem Ind Ltd et al.), Aug. 6, 1993. (Abstract).
Database WPI--Derwent Publications Ltd., London, J,A, 5197069 (Bando Chem), Aug. 6, 1993. (Abstract).
Abstract of patent, JP 5-195450 (Nitto Boseki Co. Ltd), Aug. 3, 1993.
Patent Abstracts of Japan, JP5181308 (Bando Chem Ind Ltd et al.), Jul. 23, 1993. (Abstract).
Patent Abstracts of Japan, JP 5181310 (Bando Chem Ind Ltd et al.), Jul. 23, 1993. (Abstract).
Derwent Publications Ltd., London, JP 5-132638 (Mitsubishi Kasei Corp), May 28, 1993. (Abstract).
Abstract Of Patent, JP 405132638 (Mitsubishi Kasei Corp.), May 28, 1993. (Abstract).
Derwent Publications Ltd., London, JP 5-125318 (Mitsubishi Kasei Corp), May 21, 1993. (Abstract).
Abstract Of Patent, JP 405125318 (Mitsubishi Kasei Corp.), May 21, 1993. (Abstract).
Abstract of patent, JP 05-117200 (Hidefumi Hirai et al.) (May 14, 1993).
Derwent World Patents Index, JP 5117105 (Mitsui Toatsu Chem Inc.) May 14, 1993.
Derwent Publications Ltd., London, JP 05061246 (Ricoh KK), Mar. 12, 1993. (Abstract).
Husain, N. et al. "Cyclodextrins as mobile-phase additives in reversed-phase HPLC" American Laboratory 82 80-87 1993.
Hamilton, D.P. "Tired of Shredding? New Ricoh Method Tries Different Tack" Wall Street Journal B2 1993.
"Cyclodextrins: A Breakthrough for Molecular Encapsulation" American Maize Products Co. (Amaizo) 1993.
Duxbury "The Photochemistry and Photophysics of Triphenylmethane Dyes in Solid Liquid Media" Chemical Review 93 381-433 1993).
Abstract of patent, JP 04-351603 (Dec. 7, 1992).
Abstract of patent, JP 04-351602 1992.
Derwent Publications Ltd., London, JP 404314769 (Citizen Watch Co. Ltd.), Nov. 5, 1992. (Abstract).
Abstract of patent, JP 04315739 1992.
Derwent Publications Ltd., London, JP 04300395 (Funai Denki KK, Oct. 23, 1992. (Abstract).
Derwent Publications Ltd., London, JP 404213374 (Mitsubishi Kasei Corp), Aug. 4, 1992. (Abstract).
Abstract of patent, JP 04-210228 1992.
Abstract Of Patent, JP 404202571 (Canon Inc.), Jul. 23, 1992. (Abstract).
Abstract Of Patent, JP 404202271 (Mitsubishi Kasei Corp.), Jul. 23, 1992. (Abstract).
Derwent Publications Ltd., London, JP 4-189877 (Seiko Epson Corp), Jul. 8, 1992. (Abstract).
Derwent Publications Ltd., London, JP 404189876 (Seiko Epson Corp), Jul. 8, 1992. (Abstract).
Abstract Of Patent, JP 404189877 (Seiko Epson Corp.), Jul. 8, 1992. (Abstract).
Derwent Publications Ltd., London, J,A, 4-170479 (Seiko Epson Corp), Jun. 18, 1992. (Abstract).
Abstract of patent, JP 04-81402 1992.
Abstract of patent, JP 04-81401 1992.
Kogelschatz "Silent-discharge driven excimer UV sources and their applications" Applied Surface Science 410-423 1992.
Derwent Publications, Ltd., London, JP 403269167 (Japan Wool Textile KK), Nov. 29, 1991 (Abstract).
Derwent Publications Ltd., London, JO 3247676 (Canon KK), Nov. 5, 1991 (Abstract).
Abstract of patent, JP 03-220384 1991.
Patent Abstracts of Japan, JP 03184896 (Dainippon Printing Co Ltd.) Aug. 12, 1991.
Derwent Publications Ltd., London, JP 3167270 (Mitsubishi Kasei Corp), Jul. 19, 1991. (Abstract).
Derwent Publications Ltd., London, JO 3093870 (Dainippon Ink Chem KK.), Apr. 18, 1991 (Abstract).
Abstract of patent, JP 06369890 1991.
Kogelschatz, U. et al. "New Excimer UV Sources for Industrial Applications" ABB Review 1-10 1991.
Abstract of patent, JP 03-41165 1991.
"Coloring/Decoloring Agent for Tonor Use Developed" Japan Chemical Week 1991.
Braithwaite, M., et al. "Formulation" Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints IV 11-12 1991.
Scientific Polymer Products, Inc. Brochure 24-31 1991.
Dietliker, K. "Photoiniators for Free Radical and Catioinc Polymerisation" Chem & Tech of UV & EB Formulation for Coatings, Inks & Paints III 280 1991.
Esrom et al. "Large area Photochemical Dry Etching of Polymers iwth Inocoherent Excimer UV Radiation" MRS Materials Research Society 1-7 1991.
"New Excimer UV Sources for Industrial Applications" ABB Review 391 1-10 1991.
Esrom et al. Excimer Laser-Induced Decomposition of Aluminum Nitride Materials Research Society Fall Meeting 1-6 1991.
Esrom et al. "Metal deposition with a windowless VUV excimer source" Applied Surface Science 1-5 1991.
Esrom "Excimer Laser-Induced Surface Activation of Aln for Electroless Metal Deposition" Mat. Res. Sco.lSymp. Proc. 204 457-465 1991.
Zhang et al. "UV-induced decompositin of adsorbed Cu-acetylacetonate films at room temperature for electroless metal plating" Applied Surface Science 1-6 1991.
"German company develops reuseable paper" Pulp & Paper 1991.
Abstract of patent, JP 02289652 1990.
Ohashi et al. "Molecular Mechanics Studies on Inclusion Compounds of Cyanine Dye Monomers and Dimers in Cyclodextrin Cavities," J. Am. Chem. Soc. 112 5824-5830 1990.
Kogelschatz et al. "New Incoherent Ultraviolet Excimer Sources for Photolytic Material Deposition," Laser Und Optoelektronik 1990.
Patent Abstracts of Japan, JP 02141287 (Dainippon Printing Co Ltd.) May 30, 1990.
Abstract of Patent, JP 0297957, (Fuji Xerox Co., Ltd.) 1990.
Derwent Publications Ltd., London, JP 2091166 (Canon KK), Mar. 30, 1990. (Abstract).
Esrom et al. "Metal Deposition with Incoherent Excimer Radiation" Mat. Res. Soc. Symp. Proc. 158 189-198 1990.
Esrom "UV Excimer Laer-Induced Deposition of Palladium from palladiym Acetate Films" Mat. Res. Soc. Symp. Proc. 158 109-117 1990.
Kogelschatz, U. "Silent Discharges for the Generation of ultraviolet and vacuum ultraviolet excimer radiation" Pure & Applied Chem. 62 1667-74 1990.
Esrom et al. "Investigation of the mechanism of the UV-induced palladium depositions processf from thin solid palladium acetate films" Applied Surface Science 46 158-162 1990.
Zhang et al. "VUV synchrotron radiation processing of thin palladium acetate spin-on films for metallic surface patterning" Applied Surface Science 46 153-157 1990.
Brennan et al. "Tereoelectronic effects in ring closure reactions: the 2'-hydroxychalcone--flavanone equilibrium, and related systems," Canadian J. Chem. 68 (10) pp. 1780-1785 1990.
Abstract of patent, JP 01-299083 1989.
Derwent Publications Ltd., London, J,O, 1182379 (Canon KK), Jul. 20, 1989. (Abstract).
Derwent Publications Ltd., London, JO 1011171 (Mitsubishi Chem Ind. KK.), Jan. 13, 1989 (Abstract).
Gruber, R.J., et al. "Xerographic Materials" Encyclopedia of Polymer Science and Engineering 17 918-943 1989.
Pappas, S.P. "Photocrosslinking" Comph. Pol. Sci. 6 135-148 1989.
Pappas, S.P. "Photoinitiated Polymerization" Comph. Pol. Sci. 4 337-355 1989.
Kirilenko, G.V. et al. "An analog of the vesicular process with amplitude modulation of the incident light beam" Chemical Abstracts 111 569 [No. 111:12363 3b] 1989.
Esrom et al. "UV excimer laser-induced pre-nucleation of surfaces followed by electroless metallization" Chemtronics 4 216-223 1989.
Esrom et al. "VUV light-induced deposition of palladium using an incoherent Xe2* excimer source" Chemtronics 4 1989.
Esrom et al. "UV Light-Induced Deposition of Copper Films" C5-719-C5-725 1989.
Falbe et al. Rompp Chemie Lexikon 9 270 1989.
Derwent Publications, Ltd., London, SU 1423656 (Kherson Ind Inst), Sep. 15, 1988 (Abstract).
Derwent Publications, Ltd., London, EP 0280653 (Ciba Geigy AG), Aug. 31, 1988 (Abstract).
Abstract of patent, JP 63-190815 1988.
Patent Abstracts of Japan, JP 63179985 (Tomoegawa Paper Co. Ltd.), Jul. 23, 1988.
Derwent World Patents Index, JP 63179977 (Tomoegawa Paper Mfg Co Ltd), Jul. 23, 1988.
Furcone, S.Y. et al. "Spin-on B14Sr3Ca3Cu4O16+= superconducting thin films from citrate precursors," Appl. Phys. Lett. 52(25) 2180-2182 1988.
Abstract of patent, JP 63-144329 1988.
Abstract of patent, JP 63-130164 1988.
Derwent Publications, Ltd., London, J6 3112770 (Toray Ind Inc), May 17, 1988 (Abstract).
Derwent Publications, Ltd., London, J6 3108074 (Konishiroku Photo KK), May 12, 1988 (Abstract).
Derwent Publications, Ltd., London, J6 3108073 (Konishiroku Photo KK), May 12, 1988 (Abstract).
Abstract of patent, JP 61-77846 1988.
Abstract of patent, JP 63-73241 1988.
Abstract of patent, JP 6347762, 1988.
Abstract of patent, JP 63-47763, 1988.
Abstract of patent, JP 63-47764, 1988.
Abstract of patent, JP 63-47765, 1988.
Eliasson, B., et al. "UV Excimer Radiation from Dielectric-Barrier Discharges" Applied Physics B 46 299-303 1988.
Eliasson et al. "New Trends in High Intensity UV Generation" EPA Newsletter (32) 29-40 1988.
Cotton, F.A. "Oxygen: Group Via(16)" Advanced Inorganic Chemistry 5th ed. 473-474 1988.
Derwent Publications, Ltd., London, J6 2270665 (Konishiroku Photo KK), Nov. 25, 1987 (Abstract).
Abstract of patent, JP 62-215261 1987.
Database WPI, Derwent Publications Ltd., London, JP 62032082 (Mitsubishi Denki KK), Feb. 12, 1987, (Abstract).
Abstract of patent, JP 62-32082 1987.
Derwent Publications Ltd., London, J6 2007772 (Alps Electric KK.), Jan. 14, 1987 (Abstract).
Gross et al. "Laser direct-write metallization in thin palladium acetate films" J. App. Phys. 61 (4) 1628-1632 1987.
Al-Ismail et al. "Some experimental results on thin polypropylene films loaded with finely-dispersed copper" Journal of Materials Science 415-418 1987.
Baufay et al. "Optical self-regulation during laser-induced oxidation of copper" J. Appl. Phys 61 (9) 4640-4651 1987.
Derwent Publications Ltd., London, JA 0284478 (Sanyo Chem Ind Ltd.), Dec. 15, 1986 (Abstract).
Abstract of patent, JP 61251842 1986.
Database WPI, Derwent Publications Ltd., London, GB; SU, A, 1098210 (Kutulya L A) Jun. 23, 1986.
Abstract of patent, JP 61-97025 1986.
Abstract of patent, JP 61-87760 1986.
Derwent Publications Ltd., London, DL 0234731 (Karl Marx Univ. Leipzig), Apr. 9, 1986 (Abstract).
Derwent World Patents Index, SU 1219612 (AS USSR Non-AQ Soln) Mar. 23, 1986.
Derwent Publications, Ltd., London, J6 1041381 (Osaka Prefecture), Feb. 27, 1986 (Abstract).
Dialog, JAPIO, JP 61-034057 (Ciba Geigy AG) Feb. 18, 1986.
Derwent World Patents Index, JP 61027288 (Sumitomo Chem Ind KK) Feb. 6, 1986.
Sakai et al. "A Novel and Practical Synthetic Method of 3(2H)-Furanone Derivatives," J. Heterocyclie Chem. 23 pp. 1199-1201 1986.
Jellinek, H.H.G. et al. "Evolution of H2O and CO2 During the Copper-Catalyzed Oxidation of Isotactic Polypropylene," J. Polymer Sci. 24 389-403 1986.
Jellinek, H.H.G. et al. "Diffusion of Ca2+ Catalysts from Cu-Metal Polymer or Cu-Oxide/Polymer Interfaces into Isotactic Polypropylene," J. Polymer Sci. 24 503-510 1986.
John J. Eisch and Ramiro Sanchez "Selective, Oxophilic Imination of Ketones with Bis (dichloroaluminum) Phenylimide" J. Org. Chem. 51 (10) 1848-1852 1986.
Derwent Publications Ltd., London, J6 0226575 (Sumitomo Chem Ind Ltd.), Oct. 11, 1986 (Abstract).
Abstract of patent, Jp 60-156761 1985.
Derwent Publications Ltd., London, J,A, 0011451 (Fugi Photo Film KK), Jan. 21, 1985. (Abstract).
Derwent Publications Ltd., London J6 0011-449-A (Taoka Chemical KK) Jan. 21, 1985 (abstract).
Roos, G. et al. "Textile applications of photocrosslinkable polymers" Chemical Abstracts 103 57 [No. 103:23690j] 1985.
Derwent World Patents Index, EP 127574 (Ciba Geigy AG), Dec. 5, 1984.
Derwent Publications Ltd., London, JP 0198187 (Canon KK), Nov. 9, 1984. (Abstract).
Derwent Publications Ltd., London, J,A, 0169883 (Ricoh KK), Sep. 25, 1984. (Abstract).
Derwent Publications Ltd., London, JA 0198187 (Canon KK), Sep. 11, 1984 (Abstract).
Derwent Publications Ltd., London, J.A. 0053563 (Dainippon Toryo KK), Mar. 28, 1984. (Abstract).
Derwent Publications Ltd., London, J,A, 0053562 (Dainippon Toryo KK), Mar. 28, 1984. (Abstract).
Derwent Publications Ltd., London, J,A, 0051961 (Dainippon Toryo KK), Mar. 26, 1984. (Abstract).
Abstract of Patent, JA 0051961 (Dainippon Toryo KK), Mar. 26, 1984 (Abstract).
Saenger, W. "Structural Aspects of Cyclodextrins and Their Inclusion Complexes" Inclusion Compounds--Structural Aspects of Inclusion Compounds formed by Organic Host 2 231-259 1984.
Szejtli "Industrial Applications of Cyclodextrins" Inclusion Compounds Physical Prop. & Applns. 3 331-390 1984.
Kano et al. "Three-Component Complexes of Cyclodextrins. Exciplex Formation in Cyclodextrin Cavity," J. Inclusion Phenomena 2 pp. 737-746 1984.
Suzuki et al. "Spectroscopic Investigation of Cyclodextrin Monomers, Derivatives, Polymers and Azo Dyes," J. Inclusion Phenomena 2, pp. 715-724 1984.
Abstract of patent, JA 0222164 (Ricoh KK), Dec. 23, 1983 (Abstract).
Abstract of patent, JP 58211426 (Sekisui Plastics KK), (Dec. 8, 1983).
Derwent Publications, Ltd., London, EP 0072775 (Ciba Geigy AG), Feb. 23, 1983 (Abstract).
van Beek, H.C.A "Light-Induced Colour Changes in Dyes and Materials" Color. Res. and Appl. 8 176-181 1983.
Connors, K.A. "Application of a stoichiometric model of cyclodextrin complex formation" Chemical Abstracts 98 598 [No. 98:53067g] 1983.
Abstract of Patent, EP 0065617 (IBM Corp.), Dec. 1, 1982 (Abstract).
Derwent Publications Ltd., London, J,A, 0187289 (Honshu Paper Mfg KK), Nov. 17, 1982. (Abstract).
Abstract of Patent, JA 0187289 (Honsho Paper Mfg KK), Nov. 17, 1982. (Abstract).
Abstract of Patent, JA 0185364 (Ricoh KK), Nov. 15, 1982 (Abstract).
Derwent Publications, Ltd., London J5 7139-146 (Showa Kako KK) Aug. 27, 1982(abstract).
Abstract of Patent, JA 0090069 (Canon KK), Jun. 4, 1982 (Abstract).
Derwent Publications, Ltd., London, JA 0061785 (Nippon Senka KK), Apr. 14, 1982 (Abstract).
Fischer, "Submicrosopic contact imaging with visible light by energy transfer" Appl. Phys. Letter 40(3) 1982.
Abstract of Patent, JA 0010659 (Canon KK), Jan. 2, 1982 (Abstract).
Abstract of Patent, JA 0010661 (Canon KK), Jan. 2, 1982 (Abstract),
Christen "Carbonylverbindungen: Aldehyde und Ketone," Grundlagen der Organischen Chemie 255 1982.
Derwent Publications Ltd., London, J,A, 0155263 (Canon KK), Dec. 1, 1981. (Abstract).
Abstract of Patent, JA 0155263 (Canon KK), Dec. 1, 1981 (Abstract).
Abstract of Patent, JA 0147861 (Canon KK), Nov. 17, 1981 (Abstract).
Derwent Publications Ltd., London, J,A, 0143273 (Canon KK), Nov. 7, 1981. (Abstract).
Abstract of Patent, JA 0143272 (Canon KK), Nov. 7, 1981 (Abstract).
Abstract of Patent, JA 0136861 (Canon KK), Oct. 26, 1981 (Abstract).
Abstract of Patent, JA 6133378 (Canon KK), Oct. 19, 1981 (Abstract).
Abstract of Patent, JA 6133377 (Canon KK), Oct. 19, 1981 (Abstract).
Abstract of Patent, JA 6093775 (Canon KK), Jul. 29, 1981 (Abstract).
Derwent Publications Ltd., London, J,A, 0008135 (Ricoh KK), Jan. 27, 1981. (Abstract).
Derwent Publications Ltd., London, J,A, 0004488 (Canon KK), Jan. 17, 1981. (Abstract).
Abstract of Patent, JA 0004488 (Canon KK), Jan. 17, 1981 (Abstract).
Kirk-Othmer "Metallic Coatings," Encyclopedia of Chemical Technology 15 241-274 1981.
Komiyama et al. "One-Pot Preparation of 4-Hydroxychalcone .beta.-Cyclodextrin as Catalyst," Makromol. Chem. 2 733-734 1981.
Derwent Publications, Ltd., London CA 1086-719 (Sherwood Medical) Sep. 30, 1980 (abstract).
Rosanske et al. "Stoichiometric Model of Cyclodextrin Complex Formation" Journal of Pharmaceutical Sciences 69 564-567 (5) 1980.
Semple et al. "Synthesis of Functionalized Tetrahydrofurans," Tetrahedron Letters 81 pp. 4561-4564 1980.
Kirk-Othmer "Film Deposition Techniques," Encyclopedia of Chemical Technology 10 247:283 1980.
Derwent World Patents Index, Derwent Info. Ltd., JP 54158941 (Toyo Pulp KK), Dec. 15, 1979. (Abstract).
Derwent World Patents Index, JP 54117536 (Kawashima F) Sep. 12, 1979.
Derwent Publications Ltd., London, J,A, 0005422 (Fuji Photo Film KK), Jan. 16, 1979. (Abstract).
Drexhage et al. "Photo-bleachable dyes and processes" Research Disclosure 85-87 1979.
"Color imaging devices and color filter arrays using photo-bleachable dyes" Research Disclosure 22-23 1979.
Wolff, N.E., et al. "Electrophotography" Kirk-Othmer-Encyclopedia of Chemical Technology 8 794-826 1979.
Derwent Publications Ltd., London, J,A, 0012037 (Pentel KK), Jan. 29, 1977. (Abstract).
Abstract of Patent, JA 0012037 (Pentel KK), Jan. 29, 1977 (Abstract).
Jenkins P.W. et al. "Photobleachable dye material" Research Disclosure 18 [No. 12932] 1975.
Lamberts, R.L. "Recording color grid patterns with lenticules" Research Disclosure 18-19 [No. 12923] 1975.
Karmanova, L.S. et al. "Light stabilizers of daytime fluorescent paints" Chemical Abstracts 82 147 [No. 59971p] 1975.
Prokopovich, B. et al. "Selection of effective photoinducers for rapid hardening of polyester varnish PE-250" Chemical Abstracts 83 131 [no 81334a] 1975.
"Variable Contrast Printing System" Research Disclosure 19 [No. 12931] 1975.
Lakshman "Electronic Absorption Spectrum of Copper Formate Tetrahydrate" Chemical Physics Letters 31 (2) 331-334 1975.
Derwent Publications, Ltd., London J4 9131-226 (TNational Cash Register C) Dec. 16, 1974 (abstract).
Chang, I.F., et al. "Color Modulated Dye Ink Jet Printer" IBM Technical Disclosure Bulletin 17(5) 1520-1521 1974.
"Darocur 1173: Liquid Photoiniator for Ultraviolet Curing of Coatings" 1974.
Hosokawa et al. "Ascofuranone, an antibiotic from Ascochyta," Japan Kokai 73 91,278 (Nov. 28, 1973) Merck Index 80 p. 283; abstract 94259t 1974.
Abstract of patent, NL 7112489 (Dec. 27, 1971).
Gafney et al. "Photochemical Reactions of Copper (II)--1,3-Diketonate Complexes" Journal of the Americqal Chemical Society 1971.
Derwent Publications, Ltd., London SU 292698-S Jan. 15, 1971 (abstract).
Derwent World Patent Index,CS 120380 (Kocourek, Jan) Oct. 15, 1966.
Rigdon, J.E. "In Search of Paper that Spies Can't Copy" Wall Street Journal.
Chatterjee, S. et al. "Photochemistry of Carbocynanine Alkyltriphenylborate Salts: Intra-Ion-Pair Electron Transfer and the Chemistry of Boranyl Radicals" J. Am. Chem. Soc. 112 6329-6338.
"Assay--Physical and Chemical Analysis of Complexes" Amaizo.
"Cyclodextrin" Amaizon.
"Beta Cyclodextrin Polymer (BCDP)" Amaizo.
"Chemically Modified Cyclodextrins" Amaizo.
"Cyclodextrin Complexation" American Maize Products Co.
"Monomers" Scientific Polymer-Products Inc.
Suppan, Paul "Quenching of Excited States" Chemistry and Light 65-69.
Yamaguchi, H. et al. "Supersensitization, Aromatic ketones as supersensitizers" Chemical Abstracts 53 107 (d).
Stecher, H. "Ultraviolet-absorptive additives in adhesives, lacquers and plastics" Chemical Abstracts 53 14579 (c).
Maslennikov, A.S. "Coupling of diazonium salts with ketones" Chemical Abstracts 60 3128e.
Derwent Publications Ltd., London, 4 9128022.
Abstract of Patent, JP 405195450.
Rose, Philip I. "Gelatin," Encyclopedia of Chemical Technology 7 488-513.

Primary Examiner: Berman; Susan W.
Attorney, Agent or Firm: Jones & Askew, LLP

Parent Case Text

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation application of U.S. Ser. No. 08/625,737 filed Mar. 29, 1996, now abandoned, which is a continuation-in-part application of U.S. Ser. No. 08/537,593 filed Oct. 2, 1995, now abandoned which is incorporated herein by reference, which is a continuation-in-part of U.S. patent application Ser. No. 08/463,188, filed Jun. 5, 1995, now U.S. Pat. No. 5,739,175, which is incorporated herein by reference, which is a continuation-in-part of U.S. Ser. No. 08/327,077, filed Oct. 21, 1994, now abandoned which is incorporated herein by reference, which is a continuation-in-part application of U.S. Ser. No. 08/268,685, filed Jun. 30, 1994, now abandonded which is herein incorporated by reference.

Claims

What is claimed is:

1. A wavelength specific photoreactor comprising one or more wavelength-specific sensitizing moieties covalently bonded to one or more reactive species-generating photoinitiating moieties,

wherein each photoinitiating moiety of the photoreactor is derived from a photoinitiator represented by one of the following formulae: ##STR34## wherein each sensitizing moiety of the photoreactor is derived from a chalcone, benzilidene acetone, or phthaloylglycine; and wherein the photoreactor contains more than one sensitizing moiety or more than one photoinitiating moiety.

2. The wavelength specific photoreactor of claim 1, wherein the one or more reactive species-generating photoinitiating moieties are covalently bonded to the one or more wavelength-specific sensitizing moieties by one or more spacer groups bonded to the photoinitiating moieties, sensitizing moieties or both.

3. The wavelength specific photoreactor of claim 2, wherein the one or more spacer groups comprise a carboxylic acid group, an aldehyde group, an amino group, a haloalkyl group, a hydroxyl group, or a thioalkyl group prior to covalent bonding.

4. The wavelength specific photoreactor of claim 2, wherein two sensitizing moieties are covalently bonded to one photoinitiating moiety.

5. The wavelength specific photoreactor of claim 4, wherein the photoreactor is represented by the following formula ##STR35## wherein R is a hydroxyl group, methyl group, ethyl group, or propyl group.

6. The wavelength specific photoreactor of claim 4, wherein the photoreactor is represented by the following formula ##STR36##

7. A method of generating a reactive species, comprising providing a wavelength specific photoreactor comprising one or more wavelength-specific sensitizing moieties covalently bonded to one or more reactive species-generating photoinitiating moieties, wherein each photoinitiating moiety is derived from a photoinitiator represented by one of the following formulae: ##STR37## wherein each sensitizing moiety is derived from a chalcone, benzilidene acetone, or phthaloylglycine; and wherein the photoreactor contains more than one sensitizing moiety or more than one photoinitiating moiety; and

irradiating the photoreactor.

8. The method of claim 7, wherein the one or more reactive species-generating photoinitiating moieties are covalently bonded to the one or more wavelength-specific sensitizing moieties by one or more spacer groups bonded to the photoinitiating moieties, sensitizing moieties or both.

9. The method of claim 8, wherein the one or more spacer groups comprise a carboxylic acid group, an aldehyde group, an amino group, a haloalkyl group, a hydroxyl group, or a thioalkyl group prior to covalent bonding.

10. The method of claim 8, wherein two sensitizing moieties are covalently bonded to one photoinitiating moiety.

11. The method of claim 10, wherein the wavelength specific photoreactor is represented by the following formula ##STR38## wherein R is a hydroxyl group, methyl group, ethyl group, or propyl group.

12. The method of claim 10, wherein the wavelength specific photoreactor is represented by the following formula ##STR39##

13. A photoreactor comprising at least one wavelength-specific sensitizing moiety covalently bonded to at least one reactive species-generating photoinitiating moiety, said photoreactor being represented by the following formula:

(PM).sub.x (L).sub.z (SM).sub.y

wherein SM represents the wavelength-specific sensitizing moiety, PM represents the photoinitiating moiety; L is a spacer group; x and y are independently 1 or 2; x+y is equal to three; z is equal to 0 or 1; and wherein PM is ##STR40##

14. The photoreactor of claim 13, wherein L comprises a carboxylic acid group, an aldehyde group, an amino group, a haloalkyl group, a hydroxyl group, or a thioalkyl group prior to covalent bonding.

15. A photoreactor comprising at least one wavelength-specific sensitizing moiety covalently bonded to at least one reactive species-generating photoinitiating moiety, said photoreactor being represented by the following formula:

(PM).sub.x (L).sub.z (SM).sub.y

wherein SM represents the wavelength-specific sensitizing moiety, PM represents the photoinitiating moiety; L is a spacer group; x and y are independently 1 or 2; x+y is equal to three; z is equal to 0 or 1; and wherein SM comprises a chalcone, benzilidene acetone, or phthaloylglycine.

16. The photoreactor of claim 15, wherein L comprises a carboxylic acid group, an aldehyde group, an amino group, a haloalkyl group, a hydroxyl group, or a thioalkyl group prior to covalent bonding.

17. A method of polymerizing an unsaturated polymerizable material, comprising irradiating an admixture of an unsaturated polymerizable material and the wavelength specific photoreactor of claim 1.

18. A polymer film, produced by the process of:

providing an admixture of an unsaturated polymerizable material and the wavelength specific photoreactor of claim 1 that has been drawn into a film; and

irradiating the film with an amount of radiation sufficient to polymerize the admixture.

19. A polymer-coated nonwoven web, produced by the process of:

providing a nonwoven web coated with an admixture of unsaturated polymerizable material and the wavelength specific photoreactor of claim 1; and

irradiating the coated web with an amount of radiation sufficient to polymerize the admixture.

20. A polymer-coated fiber, produced by the process of:

providing a fiber coated with an admixture of unsaturated polymerizable material and the wavelength specific photoreactor of claim 1; and

irradiating the coated fiber with an amount of radiation sufficient to polymerize the admixture.

21. A method of preparing a polymer film, comprising:

providing an admixture of unsaturated polymerizable material and the wavelength specific photoreactor of claim 1 that has been drawn into a film; and

irradiating the film with an amount of radiation sufficient to polymerize the admixture.

22. A method of coating a nonwoven web comprising:

providing a nonwoven web coated with an admixture of unsaturated polymerizable material and the wavelength specific photoreactor of claim 1; and

irradiating the coated web with an amount of radiation sufficient to polymerize the admixture.

23. A method of coating a fiber, comprising:

providing a fiber coated with an admixture of unsaturated polymerizable material and the wavelength specific photoreactor of claim 1; and

irradiating the coated fiber with an amount of radiation sufficient to polymerize the admixture.

24. An adhesive composition comprising:

an unsaturated polymerizable material admixed with the wavelength specific photoreactor of claim 1,

wherein the adhesive is polymerizable upon exposure to radiation.

25. A laminated structure comprising at least two layers bonded together with an adhesive composition, in which at least one layer is a cellulosic or polyolefin nonwoven web or film,

wherein the adhesive composition comprises an unsaturated polymerizable material and the wavelength specific photoreactor of claim 1, wherein the adhesive composition has been polymerized by exposure to radiation.

26. A method of laminating a structure,

providing a structure comprising at least two layers, in which at least one layer is a cellulosic or polyolefin nonwoven web or film, with an adhesive composition between said layers, and

irradiating the adhesive composition to polymerize the adhesive composition,

wherein the adhesive composition comprises an unsaturated polymerizable material admixed with the wavelength specific photoreactor of claim 1.

Description

TECHNICAL FIELD

The present invention relates to a composition and method for generating a reactive species. The present invention more particularly relates to a composition and method for generating reactive species which can be used to polymerize or photocure polymerizable unsaturated material. In particular, the present invention provides a photoreactor that absorbs radiation at a wavelength that is particularly suited to exposure to lamps that emit at substantially the same wavelength.

BACKGROUND OF THE INVENTION

The present invention relates to a method of generating a reactive species. The present invention also relates to radiation-initiated polymerization and curing processes. For convenience, much of the discussion which follows centers on free radicals as a particularly desirable reactive species. Such discussion, however, is not to be construed as limiting either the spirit or scope of the present invention.

Polymers have served essential needs in society. For many years, these needs were filled by natural polymers. More recently, synthetic polymers have played an increasingly greater role, particularly since the beginning of the 20th century. Especially useful polymers are those prepared by an addition polymerization mechanism, i.e., free radical chain polymerization of unsaturated monomers, and include, by way of example only, coatings and adhesives. In fact, the majority of commercially significant processes is based on free-radical chemistry. That is, chain polymerization is initiated by a reactive species which often is a free radical. The source of the free radicals is termed an initiator or photoinitiator.

Improvements in free radical chain polymerization have focused both on the polymer being produced and the photoinitiator. Whether a particular unsaturated monomer can be converted to a polymer requires structural, thermodynamic, and kinetic feasibility. Even when all three exist, kinetic feasibility is achieved in many cases only with a specific type of photoinitiator. Moreover, the photoinitiator can have a significant effect on reaction rate which, in turn, may determine the commercial success or failure of a particular polymerization process or product.

A free radical-generating photoinitiator may generate free radicals in several different ways. For example, the thermal, homolytic dissociation of an initiator typically directly yields two free radicals per initiator molecule. A photoinitiator, i.e., an initiator which absorbs light energy, may produce free radicals by either of two pathways:

(1) the photoinitiator undergoes excitation by energy absorption with subsequent decomposition into one or more radicals: or

(2) the photoinitiator undergoes excitation and the excited species interacts with a second compound (by either energy transfer or a redox reaction) to form free radicals from the latter and/or former compound(s).

While any free radical chain polymerization process should avoid the presence of species which may prematurely terminate the polymerization reaction, prior photoinitiators present special problems. For example, absorption of the light by the reaction medium may limit the amount of energy available for absorption by the photoinitiator. Also, the often competitive and complex kinetics involved may have an adverse effect on the reaction rate. Moreover, commercially available radiation sources, such as medium and high pressure mercury and xenon lamps, emit over a wide wavelength range, thus producing individual emission bands of relatively low intensity. Most photoinitiators only absorb over a small portion of the emission spectra and, as a consequence, most of the lamps radiation remains unused. In addition, most known photoinitiators have only moderate quantum yields (generally less than 0.4) at these wavelengths, indicating that the conversion of light radiation to radical formation can be more efficient.

Thus, there are continuing opportunities for improvements in free radical polymerization photoinitiators.

SUMMARY OF THE INVENTION

The present invention addresses some of the difficulties and problems discussed above by the discovery of an efficient composition and method for utilizing radiation. Hence, the present invention includes a compositions and methods for generating a reactive species which includes providing one or more wavelength-specific sensitizers in association with one or more reactive species-generating photoinitiators and irradiating the resulting wavelength specific photoreactor composition. One of the main advantages of the wavelength specific photoreactor composition of the present invention is that it can be used to efficiently generate reactive species under extremely low energy lamps as compared to prior art lamps.

The association of one or more wavelength-specific sensitizers with one or more reactive species-generating photoinitiators results in a structure referred to herein for convenience as a wavelength specific photoreactor composition. The present invention includes arylketoalkene wavelength-specific sensitizers. One major advantage of the wavelength specific photoreactor compositions is the use of arylketoalkene wavelength-specific sensitizers. The wavelength specific photoreactor compositions that contain the arylketoalkene wavelength-specific sensitizers efficiently absorb radiation at wavelengths between approximately 250 nm and 350 nm. Another major advantage of the wavelength specific photoreactor compositions of the present invention is that, when combined with polvmerizable material, they cause rapid curing times in comparison to the curing times of the prior art with relatively low output lamps. Yet another advantage of the of the present invention is that the multi-photoinitiator photoreactors of the present invention or the multi-wavelength specific sensitizer photoreactors have even faster curing times in comparison to the single-photoinitiator photoreactors of the present invention and/or are more sensitive than the single sensitizer photoreactors of the present invention.

The wavelength specific photoreactor compositions of the present invention also differ from the prior art in that the prior art sensitizers absorb a band width of radiation, whereas the sensitizer of the present invention absorbs a substantially single wavelength. The use of a wavelength specific photoreactor composition capable of absorbing a substantially single wavelength of radiation results in an extremely efficient photoreactor upon exposure to a very narrow bandwidth of radiation or upon exposure to a single wavelength of radiation.

The present method involves effectively tuning the energy-absorbing entity, referred to herein as a wavelength specific photoreactor composition, to efficiently utilize an emitted band of radiation. The wavelength-specific sensitizer effectively absorbs photons and efficiently transfers the absorbed energy to a photoinitiator which, in turn, generates a reactive species. The wavelength-specific sensitizer is adapted to have an absorption peak generally corresponding to a maximum emission band of the radiation source.

The present invention includes various combinations of wavelength-specific sensitizers and photoinitiators. By varying the combination, one can effectively increase the number of photoinitiators per wavelength specific photoreactor composition or effectively increase the number of wavelength-specific sensitizers per photoreactive composition.

The present invention also includes a method of polymerizing an unsaturated monomer by exposing the unsaturated monomer to radiation in the presence of the efficacious wavelength specific photoreactor composition described above. When an unsaturated oligomer/monomer mixture is employed in place of the unsaturated monomer, curing is accomplished.

The present invention further includes a film and a method for producing a film, by drawing an admixture of unsaturated polymerizable material and the wavelength specific photoreactor composition of the present invention, into a film and irradiating the film with an amount of radiation sufficient to polymerize the composition. When the unsaturated polymerizable material is an unsaturated oligomer/monomer mixture, curing is accomplished. The admixture may be drawn into a film on a nonwoven web or on a fiber, thereby providing a polymer-coated nonwoven web or fiber, and a method for producing the same.

The film can be a film containing a dye or a pigment and can be used in the printing industry. The film with the dye or pigment therein is applied to a substrate such as paper and is then exposed to a source of electromagnetic radiation at the appropriate wavelength thereby causing the film to be cured. The use of the present invention in the printing industry has several advantages including increased printing speeds, lower energy consumption, and lower heat production.

The present invention also includes an adhesive composition comprising an unsaturated polymerizable material admixed with the wavelength specific photoreactor composition of the present invention. Similarly, the present invention includes a laminated structure comprising at least two layers bonded together with the above described adhesive composition, in which at least one layer is a cellulosic or polyolefin nonwoven web or film. Accordingly, the present invention provides a method of laminating a structure wherein a structure having at least two layers with the above described adhesive composition between the layers is irradiated to polymerize the adhesive composition. When the unsaturated polymerizable material in the adhesive is an unsaturated oligomer/monomer mixture, the adhesive is irradiated to cure the composition.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagrammatic representation of the excimer lamp employed in some of the examples.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to the unexpected discovery of an efficient reactive species-generating composition and methods for utilizing the same. More particularly, the present invention includes a composition and method for generating a reactive species which includes providing one or more wavelength-specific sensitizers in association with one or more reactive species-generating photoinitiators and irradiating the wavelength-specific sensitizer. The association of one or snore wavelength-specific sensitizers with one or more reactive species-generating photoinitiators results in a structure referred to herein for convenience as a wavelength specific photoreactor composition.

The present invention also includes a method of polymerizing an unsaturated polymerizable material by exposing the unsaturated material to radiation in the presence of the efficacious wavelength specific photoreactor composition described above. Further, the present invention includes a film and a method for producing a film, by drawing an admixture of unsaturated polymerizable material and the wavelength specific photoreactor composition of the present invention, into a film and irradiating the film with an amount of radiation sufficient to polymerize the composition.

The film can be a film containing a dye or a pigment and can be used in the printing industry. The film with the dye or pigment therein is applied to a substrate such as paper and is then exposed to a source of electromagnetic radiation at the appropriate wavelength thereby causing the film to be cured. The use of the present invention in the printing industry has several advantages including increased printing speeds, lower energy consumption, and lower heat production.

Also, the present invention includes an adhesive composition comprising an unsaturated polymerizable material admixed with the wavelength specific photoreactor composition of the present invention. Similarly, the present invention includes a laminated structure comprising at least two layers bonded together with the above described adhesive composition, in which at least one layer is a cellulosic or polyolefin nonwoven web or film. Accordingly, the present invention provides a method of laminating a structure wherein a structure having at least two layers with the above described adhesive composition between the layers is irradiated to polymerize the adhesive composition.

The wavelength specific photoreactor composition of the present invention will be described in detail below, followed by a detailed description of the method of generating reactive species, and the various representative applications of the method.

The wavelength specific photoreactor composition of the present invention is one or more wavelength-specific sensitizers associated with one or more reactive species-generating photoinitiators. Accordingly, the term "wavelength specific photoreactor composition" is used herein to mean one or more wavelength-specific sensitizers associated with one or more reactive species-generating photoinitiators. In an embodiment where the sensitizer(s) is admixed with the photoinitiator(s), the term "wavelength specific photoreactor composition" is used to mean the admixture. In the embodiment where the sensitizer(s) are covalently bonded to the photoinitiator(s), the term "wavelength specific photoreactor composition" is used to mean the resultant molecule. The term "single-photoinitiator photoreactor" is used to mean a wavelength specific photoreactor composition having one reactive species-generating photoinitiator therein. The term "multi-photoinitiator photoreactor" is used to mean a wavelength specific photoreactor composition having more than one reactive species-generating photoinitiator. Therefore, it follows that the term "double-photoinitiator photoreactor" is used to mean a wavelength specific photoreactor composition having two reactive species-generating photoinitiators. The present invention also contemplates a wavelength specific photoreactor wherein there is a single reactive species-generating photoinitiator and multiple wavelength-specific sensitizers. Accordingly, the term "double-sensitizer photoreactor" is used to mean a wavelength specific photoreactor composition having two wavelength-specific sensitizers. Finally, the present invention includes wavelength specific photoreactor compositions with multiple wavelength specific sensitizers and multiple reactive species-generating photoinitiators.

The term "associated" as used herein is meant to include any means which results in the wavelength-specific sensitizer(s) and the reactive species-generating photoinitiator(s) being in sufficiently close proximity to each other to permit the transfer of energy absorbed by the sensitizer(s) to the photoinitiator(s). For example, the wavelength-specific sensitizer(s) and the reactive species-generating photoinitiator(s) may be bonded to each other or to a spacer molecular as described hereinafter by covalent, hydrogen, van der Waals, or ionic bonds. Alternatively, the sensitizer(s) and the photoinitiator(s) may be physically admixed.

The term "wavelength-specific sensitizer" is used herein to mean that the sensitizer is adapted to have an absorption wavelength band generally corresponding to an emission peak of the radiation. Either or both of the sensitizer and the radiation may have more than one absorption wavelength band and emission peak, respectively. In the event both the sensitizer and the radiation have more than one absorption wavelength band and emission peak, respectively, the general correspondence just described need not be limited to a single absorption wavelength band and a single emission peak.

According to the present invention, a desirable "wavelength-specific sensitizer" is an arylketoalkene wavelength-specific sensitizer having the following general formula: ##STR1## wherein R.sub.1 is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;

R.sub.2 is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group;

R.sub.3 is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or a heteroaryl group; and

R.sub.4 is an aryl, heteroaryl, or substituted aryl group.

Desirable sensitizer produced by the process of dehydrating a tertiary alcohol that is alpha to a carbonyl group on a sensitizer is represented in the following general formula: ##STR2## wherein when R.sub.1 is an aryl group, R.sub.2 is a hydrogen; alkyl; aryl; heterocyclic; or phenyl group, the phenyl group optionally being substituted with an alkyl, halo, amino, or thiol group; and wherein when R.sub.2 is an aryl group, R.sub.1 is a hydrogen; alkyl; aryl; heterocyclic; or phenyl group, the phenyl group optionally being substituted with an alkyl, halo, amino, or thiol group. Preferably, the alkene group is in the trans configuration. The wavelength-specific sensitizer of the present invention contains an aryl group, a carbonyl group, and a double bond (alkene group), in any order, such that resonance of the unshared electrons occurs.

Desirably, the arylketoalkene sensitizer is a chalcone having the following formula: ##STR3## which efficiently absorbs radiation having a wavelength at about 308 nanometers, or is benzylideneacetone (4-phenyl-3-buten-2-one) having the following formula: ##STR4## which efficiently absorbs radiation having a wavelength at about 280 nanometers. Desirably, the sensitizer of the present invention is in the trans configuration with respect to the double bond. However, the sensitizer may also be in the cis configuration across the double bond.

Although the above sensitizers are desirable, any sensitizer known in the art capable of absorbing photons having a substantially specific wavelength and transferring the absorbed energy to an associated reactive-species generating photoinitiator may be used in the present wavelength specific photoreactor compositions. As a practical matter, two classes of compounds are known to be useful as wavelength-specific sensitizers, namely, phthalic acid derivatives and phenyl-substituted aliphatic ketones. A particularly useful example of each class is phthaloylglycine and 4-(4-hydroxyphenyl)butan-2-one, respectively. Therefore, another desirable sensitizer is phthaloylglycine having the following formula: ##STR5##

As stated above, the wavelength-specific sensitizer of the present invention may optionally be covalently bonded to one or more reactive species-generating photoinitiators. In that embodiment, the aryl group of a wavelength-specific sensitizer of the present invention can contain a group including, but not limited to, a carboxylic acid group, an aldehyde group, an amino group, a haloalkyl group, a hydroxyl group, or a thioalkyl group attached thereto to allow the arylketoalkene to be covalently bonded to the other molecule. Accordingly, a desired arylketoalkene reactive compound includes the following: ##STR6##

Although it is preferred that the group attached to the aryl group is para to the remainder of the reactive molecule, the group may also be ortho or meta to the remainder of the molecule. Note that the di-carboxylic acid substituted chalcone type compound shown above can be covalently bonded to two photoinitiators, one photoinitiator on each aryl group substituted with a carboxylic acid group, thereby producing a double-photoinitiator photoreactor.

In the embodiment where the sensitizer is phthaloylglycine, and two photoinitiators are covalently bonded thereto, the phenyl group will contain a group including, but limited to, a carboxylic acid group, an aldehyde group, an amino group, a haloalkyl group, a hydroxyl group, or a thioalkyl group attached thereto to allow the phthaloylglycine to be covalently bonded to one photoinitiator. Of course, the carboxylic acid group in the phthaloylglycine provides the second location for covalently bonding to the second photoinitiator.

The term "reactive species" is used herein to mean any chemically reactive species including, but not limited to, free-radicals, cations, anions, nitrenes, and carbenes. Illustrated below are examples of several of such species. Examples of carbenes include, for example, methylene or carbene, dichlorocarbene, diphenylcarbene, alkylcarbonylcarbenes, siloxycarbenes, and dicarbenes. Examples of nitrenes include, also by way of example, nitrene, alkyl nitrenes, and aryl nitrenes. Cations (sometimes referred to as carbocations or carbonium ions) include, by way of illustration, primary, secondary, and tertiary alkyl carbocations, such as methyl cation, ethyl cation, propyl cation, t-butyl cation, t-pentyl cation, t-hexyl cation; allylic cations; benzylic cations; aryl cations, such as triphenyl cation; cyclopropylmethyl cations; methoxymethyl cation; triarylsulphonium cations; and acyl cations. Cations also include those formed from various metal salts, such as tetra-n-butylammonium tetrahaloaurate(III) salts; sodium tetrachloroaurate(III); vanadium tetrachloride; and silver, copper(I) and (II), and thallium(I) triflates. Examples of anions (sometimes referred to as carbanions) include, by way of example, alkyl anions, such as ethyl anion, npropyl anion, isobutyl anion, and neopentyl anion; cycloalkyl anions, such as cyclopropyl anion, cyclobutyl anion, and cyclopentyl anion; allylic anions; benzylic anions; aryl cations; and sulfur- or phosphorus-containing alkyl anions. Finally, examples of organometallic photoinitiators include titanocenes, fluorinated diaryltitanocenes, iron arene complexes, manganese decacarbonyl, and methylcyclopentadienyl manganese tricarbony. Organometallic photoinitiators generally produce free radicals or cations.

Any reactive species-generating photoinitiator may be used which generates the desired reactive species. With regard to the free radical-generating photoinitiators, these photoinitiators may be any of the photoinitiators known to those having ordinary skill in the art. The largest group of photoinitiators are carbonyl compounds, such as ketones, especially .alpha.-aromatic ketones. Examples of .alpha.-aromatic ketone photoinitiators include, by way of illustration only, benzophenones; xanthones and thioxanthones; .alpha.-ketocoumarins; benzils; .alpha.-alkoxydeoxybenzoins; benzil ketals or .alpha.,.alpha.-dialkoxydeoxybenzoins; enzoyldialkylphosphonates; acetophenones, such as .alpha.-hydroxycyclohexyl phenyl ketone, .alpha.,.alpha.-dimethyl-.alpha.-hydroxyacetophenone, .alpha.,.alpha.-dimethyl-.alpha.-morpholino-4-methylthio-acetophenone, .alpha.-ethyl-.alpha.-benzyl-.alpha.-dimethylaminoacetophenone, .alpha.-ethyl-.alpha.-benzyl-.alpha.-dimethylamino-4-morpholinoacetophenon e, .alpha.-ethyl-.alpha.-benzyl-.alpha.-dimethylamino-3,4-dimethoxyacetopheno ne, .alpha.-ethyl-.alpha.-benzyl-.alpha.-dimethylamino-4-methoxyacetophenone, .alpha.-ethyl-.alpha.-benzyl-.alpha.-dimethylamino-4-dimethylaminoacetophe none, .alpha.-ethyl-.alpha.-benzyl-.alpha.-dimethylamino-4-methylacetophenone, .alpha.-ethyl-.alpha.-(2-propenyl)-.alpha.-dimethylamino-4-morpholinoaceto phenone, .alpha.,.alpha.-bis(2-propenyl)-.alpha.-dimethylamino-4-morpholinoacetophe none, .alpha.-methyl-.alpha.-benzyl-.alpha.-dimethylamino-4-morpholinoacetopheno ne, and .alpha.-methyl-.alpha.-(2-propenyl)-.alpha.-dimethylamino-4-morpholinoacet o-phenone; .alpha.,.alpha.-dialkoxyaceto-phenones; .alpha.-hydroxyalkylphenones; O-acyl .alpha.-oximino ketones; acylphosphine oxides; fluorenones, such as fluorenone, 2-t-butylperoxycarbonyl-9-fluorenone, 4-t-butylperoxyvarbonyl-nitro-9-fluorenone, and 2,7-di-t-butylperoxy-carbonyl-9-fluorenone; and .alpha.- and .beta.-naphthyl carbonyl compounds. Other free radical generating photoinitiators include, by way of illustration, triarylsilyl peroxides, such as triarylsilyl t-butyl peroxides; acylsilanes; and some organometallic compounds. The free radical-generating initiator desirably will be an acetophenone. More desirably, the photoinitiator will be IRGACURE.RTM.-2959 (1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one or 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone).

The types of reactions that various reactive species enter into include, but are not limited to, addition reactions, including polymerization reactions; abstraction reactions; rearrangement reactions: elimination reactions, including decarboxylation reactions; oxidation-reduction (redox) reactions; substitution reactions; and conjugation/deconjugation reactions.

In the embodiments where one or more wavelength-specific sensitizers are bound to one or more reactive species-generating photoinitiators, any suitable method that is known in the art may be used to bond the sensitizer(s) to the photoinitiator(s). The choice of such method will depend on the functional groups present in the sensitizers and photoinitiators and is readily made by those having ordinary skill in the art. Such bonding may be accomplished by means of functional groups already present in the molecules to be bonded, by converting one or more functional groups to other functional groups, by attaching functional groups to the molecules, or through one or more spacer molecules.

Examples 1-3 herein describe methods of preparing the arylketoalkene sensitizer of the present invention, and covalently bonding it to a photoinitiator, namely IRGACURE.RTM.-2959. The reaction described in Example 3 may be used on any arylketoalkene sensitizer of the present invention having a carboxylic acid functional group on R.sub.1 or R.sub.2 whichever is the aryl group. This reaction of any arylketoalkene sensitizer is represented by the formula below, wherein R.sub.3 represents the remainder of the arylketoalkene sensitizer of the present invention, and wherein the carboxylic acid group is attached to R.sub.1 and/or R.sub.2 : ##STR7##

In the embodiment where both R.sub.1 and R.sub.2 are phenyl groups, if a carboxylic acid group is attached to only one of the phenyl groups, a single-photoinitiator photoreactor is produced. In the embodiment where both R.sub.1 and R.sub.2 are phenyl groups, and a carboxylic acid group is attached to both phenyl groups, a double-photoinitiator photoreactor is produced.

Desirably, the wavelength specific photoreactor composition of the present invention is represented by the to following formula: ##STR8##

More desirably, the wavelength specific photoreactor composition of the present invention is represented by the following formulas: ##STR9##

Another wavelength specific photoreactor composition that is considered part of the present invention is the compound represented by the following formula: ##STR10##

Synthesis of this wavelength specific photoinitiator composition is described in Examples 9 through 12 herein.

Another wavelength specific photoreactor composition of the present invention is a "double-photoinitiator photoreactor" or a "double-sensitizer photoreactor". These compositions, for example the double-photoinitiator or the double-sensitizer photoreactor compositions, are generally more sensitive to the electromagnetic radiation and are useful in situations were increased sensitivity is required. Although not wanting to be limited by the following, it is theorized that the double-photoinitiator photoreactor is more sensitive as more reactive species are generated per photon absorbed than if the photoreactor contained only one reactive-species generating photoinitiator. Also, although not wanting to be limited by the following, it is theorized that the double-sensitizer photoreactor is more likely to absorb a photon of radiation than a single-sensitizer photoreactor as the double-sensitizer photoreactor contains two sensitizers, and therefore in situations where there is little light present, such a double-sensitizer photoreactor is more likely to absorb radiation than a photoreactor having only one sensitizer.

One example of a double-photoinitiator wavelength specific photoreactor composition of the present invention is represented by the following formula: ##STR11##

Example 6 herein describes a method of preparing a double carboxylic acid substituted chalcone and then the method of preparing the above double-photoinitiator photoreactor. The reaction for preparing the double-photoinitiator photoreactor described in Example 6 may be used on any sensitizer of the present invention having two carboxylic acid functional groups on each end of the sensitizer.

The method of preparing the double carboxylic acid substituted chalcone is illustrated as follows: ##STR12##

It is to be understood that any methods known to those of ordinary skill in the chemical arts may be used to prepare the above double carboxylic acid substituted chalcone, or any other double carboxylic acid substituted sensitizer. It is also to be understood that any methods known in the art may be used to prepare sensitizers that are substituted with one or more of the other functional groups listed above. It is further to be understood that the functional groups on a sensitizer may be the same or they may be different.

The method of preparing the double-photoinitiator photoreactor from the above double carboxylic acid substituted chalcone is illustrated as follows: ##STR13##

It is to be understood that the above illustrated double-photoinitiator photoreactor is specifically referred to as the "chalcone double-photoinitiator photoreactor", in contrast to other double-photoinitiators within the present invention as will be further discussed below.

As discussed above, sensitizers other than the arylketoalkene sensitizers above may be in the wavelength specific photoreactor compositions of the present invention. For example, the sensitizer phthaloylglycine may be covalently bonded to one or two photoinitiators as is illustrated below, wherein the top wavelength specific photoreactor composition is one IRGACURE.RTM.-2959 photoinitiator covalently bonded to phthaloylglycine and the bottom wavelength specific photoreactor composition is two IRGACURE.RTM.-2959 photoinitiators covalently bonded to phthaloylclycine. ##STR14##

Another wavelength specific photoreactor composition of the present intention is a "double-wavelength specific sensitizer photoreactor". One example of this double-wavelength specific photoreactor composition is represented by the following formula: ##STR15##

Synthesis of this wavelength specific photoinitiator composition is shown in Examples 13 through 17 herein. Another double-wavelength specific sensitizer photoreactor of the present invention comprises the compound represented by the following formula: ##STR16##

It is to be understood that "R" is preferably a hydroxyl group, but it can be an alkyl group including, but not limited to, a methyl, ethyl or propyl group. The important feature of the reactive species generating portion of the molecule is the tertiary carbon atom that is in the alpha position to the carboxyl group.

It is to be understood that the above reactions are merely one method of binding a one or more wavelength sensitizers to one or more photoinitiators, and that other methods known in the art may be used.

The term "spacer molecule" is used herein to mean any molecule which aids in the bonding process. For example, a spacer molecule may assist in the bonding reaction by relieving steric hindrance. Alternatively, a spacer molecule may allow use of more reactive or more appropriate functional groups, depending upon the functional groups present in the sensitizer and photoinitiator. It is contemplated that a spacer molecule may aid in the transfer of energy from the sensitizer to the photoinitiator, by either allowing a more favorable conformation or providing a more favorable energy transfer pathway.

As noted earlier, the wavelength-specific sensitizer is adapted to have an absorption wavelength band generally corresponding to an emission peak of the radiation. In addition, the wavelength-specific sensitizer will have a high intensity of absorption. For example, the wavelength-specific sensitizer may have a molar extinction coefficient greater than about 2,000 liters per mole per cm (1 mole.sup.-1 cm.sup.-1) at an absorption maximum. As another example, the wavelength-specific sensitizer may have a molar extinction coefficient (absorptivity) greater than about 5.000 l mole.sup.-1 cm.sup.-1. As another example, the wavelength-specific sensitizer may have a molar extinction coefficient (absorptivity) greater than about 10,000 l mole.sup.-1 cm.sup.-1. As a further example, the wavelength-specific sensitizer will have a molar extinction coefficient greater than about 20,000 l mole.sup.-1 cm.sup.-1.

The absorption characteristics of the wavelength-specific sensitizer are not limited to a single wavelength band. Many compounds exhibit more than one absorption wavelength band. Consequently, a wavelength-specific sensitizer may be adapted to absorb two or more wavelength bands of radiation. Alternatively, two or more wavelength-specific sensitizers may be associated with a reactive species-generating photoinitiator. Such two or more wavelength-specific sensitizers may absorb the same wavelength band or they may absorb two or more different wavelength bands of radiation.

The method of the present invention involves generating a reactive species by exposing a wavelength specific photoreactor composition to radiation in which the wavelength specific photoreactor composition includes a wavelength-specific sensitizer associated with one or more reactive species-generating photoinitiators. In other words, the method involves providing a wavelength-specific sensitizer in association with one or more reactive species-generating photoinitiators and irradiating the wavelength-specific sensitizer.

The term "quantum yield" is used herein to indicate the efficiency of a photochemical process. More particularly quantum yield is a measure of the probability that a particular molecule will absorb a quantum of light during its interaction with a photon. The term expresses the number of photochemical events per photon absorbed. Thus, quantum yields may vary from zero (no absorption) to 1.

The sensitizer absorbs photons having a specific wavelength and transfers the absorbed energy to an associated photoinitiator which, in turn, generates a reactive species. However, the efficiency with which a reactive species is generated is significantly greater than that experienced with the reactive species-generating photoinitiator alone. For example, the wavelength specific photoreactor composition desirably will have a quantum yield greater than about 0.5. More desirably, the quantum yield of the wavelength specific photoreactor composition will be greater than about 0.6. Even more desirably, the quantum yield of the wavelength specific photoreactor composition will be greater than about 0.7. Still more desirably, the quantum yield of the wavelength specific photoreactor composition will be greater than about 0.8, with the most desirable quantum yield being greater than about 0.9.

The term "polymerization" is used herein to mean the combining, e.g. covalent bonding, of large numbers of smaller molecules, such as monomers, to form very large molecules, i.e., macromolecules or polymers. The monomers may be combined to form only linear macromolecules or they may be combined to form three-dimensional macromolecules, commonly referred to as crosslinked polymers.

As used herein, the term "curing" means the polymerization of functional oligomers and monomers, or even polymers, into a crosslinked polymer network. Thus, curing is the polymerization of unsaturated monomers or oligomers in the presence of crosslinking agents.

The terms "unsaturated monomer," "functional oligomer," and "crosslinking agent" are used herein with their usual meanings and are well understood by those having ordinary skill in the art. The singular form of each is intended to include both the singular and the plural, i.e., one or more of each respective material.

The term "unsaturated polymerizable material" is meant to include any unsaturated material capable of undergoing polymerization. The term encompasses unsaturated monomers, oligomers, and crosslinking agents. Again, the singular form of the term is intended to include both the singular and the plural.

Exposing the wavelength specific photoreactor composition of the present invention to radiation results in the generation of one or more reactive species. Thus, the wavelength specific photoreactor composition may be employed in any situation where reactive species are required, such as for the polymerization of an unsaturated monomer and the curing of an unsaturated oligomer/monomer mixture. The unsaturated monomers and oligomers may be any of those known to one having ordinary skill in the art. In addition, the polymerization and curing media also may contain other materials as desired, such as pigments, extenders, amine synergists, and such other additives as are well known to those having ordinary skill in the art.

By way of illustration only, examples of unsaturated monomers and oligomers include ethylene, propylene, vinyl chloride, isobutylene, styrene, isoprene, acrylonitrile, acrylic acid, methacylic acid, ethyl acrylate, methyl methacrylate, vinyl acrylate, allyl methacrylate, tripropylene glycol diacrylate, trimethylol propane ethoxylate acrylate, epoxy acrylates, such as the reaction product of a bisphenol A epoxide with acrylic acid; polyester acrylates, such as the reaction product of acrylic acid with an adipic acid/hexanediol-based polyester, urethane acrylates, such as the reaction product of hydroxypropyl acrylate with diphenylmethane-4,4'-diisocyanate, and polybutadiene diacrylate oligomer.

Accordingly, the present invention also comprehends a method of polymerizing an unsaturated monomer by exposing the unsaturated monomer to radiation in the presence of the efficacious wavelength specific photoreactor composition described above. When an unsaturated oligomer/monomer mixture is employed in place of the unsaturated monomer, curing is accomplished. It is to be understood that the polymerizable material admixed with the wavelength specific photoreactor composition of the present invention is to be admixed by means known in the art, and that the mixture will be irradiated with an amount of radiation sufficient to polymerize the material. The amount of radiation sufficient to polymerize the material is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of wavelength specific photoreactor composition, the identity and amount of the polymerizable material, the intensity and wavelength of the radiation, and the duration of exposure to the radiation.

The present invention further includes a film and a method for producing a film, by drawing an admixture of unsaturated polymerizable material and the wavelength specific photoreactor composition of the present invention, into a film and irradiating the film with an amount of radiation sufficient to polymerize the composition. When the unsaturated polymerizable material is an unsaturated oligomer/monomer mixture, curing is accomplished. Any film thickness may be produced, as per the thickness of the admixture formed, so long as the admixture sufficiently polymerizes upon exposure to radiation. The admixture may be drawn into a film on a nonwoven web or on a fiber, thereby providing a polymer-coated nonwoven web or fiber, and a method for producing the same. Any method known in the art of drawing the admixture into a film may be used in the present invention. The amount of radiation sufficient to polymerize the material is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of wavelength specific photoreactor composition, the identity and amount of the polymerizable material, the thickness of the admixture, the intensity and wavelength of the radiation, and duration of exposure to the radiation.

The term "fiber" as used herein denotes a threadlike structure. The fibers used in the present invention may be any fibers known in the art. The term "nonwoven web" as used herein denotes a web-like matter comprised of one or more overlapping or interconnected fibers in a nonwoven manner. It is to be understood that any nonwoven fibers known in the art may be used in the present invention.

The present invention also includes an adhesive composition comprising an unsaturated polymerizable material admixed with the wavelength specific photoreactor composition of the present invention. Similarly, the present invention includes a laminated structure comprising at least two layers bonded together with the above described adhesive composition, in which at least one layer is a cellulosic or polyolefin nonwoven web or film. Accordingly, the present invention provides a method of laminating a structure wherein a structure having at least two layers with the above described adhesive composition between the layers is irradiated to polymerize the adhesive composition. When the unsaturated polymerizable material in the adhesive is an unsaturated oligomer/monomer mixture, the adhesive is irradiated to cure the composition.

It is to be understood that any layers may be used in the present invention, on the condition that at least one of the layers allows sufficient radiation to penetrate through the layer to enable the admixture to polymerize sufficiently. Accordingly, any cellulosic or polyolefin nonwoven web or film known in the art may be used as one of the layers so long as they allow radiation to pass through. Again, the amount of radiation sufficient to polymerize the admixture is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of wavelength specific photoreactor composition, the identity aid amount of the polymerizable material, the thickness of the admixture, the identity and thickness of the layer, the intensity and wavelength of the radiation, and the duration of exposure to the radiation.

The radiation to which the wavelength specific photoreactor composition is exposed generally will have a wavelength of from about 4 to about 1,000 nanometers. Thus, the radiation may be ultraviolet radiation, including near ultraviolet and far or vacuum ultraviolet radiation; visible radiation: and near infrared radiation. Desirably, the radiation will have a wavelength of from about 100 to about 900 nanometers. More desirably, the radiation will have a wavelength of from about 100 to 700 nanometers.

Desirably, when the reactive species-generating photoinitiator is an organic compound, the radiation will be ultraviolet radiation having a wavelength of from about 4 to about 400 nanometers. More desirably, the radiation will have a wavelength of from about 100 to about 375 nanometers, and even more desirably will have a wavelength of from 200 to about 370 nanometers. For example, the radiation may have a wavelength of from about 222 to about 308 nanometers. The radiation desirably will be incoherent, pulsed ultraviolet radiation from a dielectric barrier discharge excimer lamp.

Excimers are unstable excited-state molecular complexes which occur only under extreme conditions, such as those temporarily existing in special types of gas discharge. Typical examples are the molecular bonds between two rare gaseous atoms or between a rare gas atom and a halogen atom. Excimer complexes dissociate within less than a microsecond and, while they are dissociating, release their binding energy in the form of ultraviolet radiation. The dielectric barrier excimers in general emit in the range of from about 125 nm to about 500 nm, depending upon the excimer gas mixture.

Dielectric barrier discharge excimer lamps (also referred to hereinafter as "excimer lamp") are described, for example, by U. Kogelschatz. "Silent discharges for the generation of ultraviolet and vacuum ultraviolet excimer radiation." Pure & Appl. Chem. 62. No. 9, pp. 16671674 (1990); and E. Eliasson and U. Kogelschatz, "UV Excimer Radiation from Dielectric-Barrier Discharges." Appl. Phys. B. 46, pp. 299-303 (1988). Excimer lamps Were developed by ABB Infocom Ltd., Lenzburg, Switzerland and at the present time are available from Heraeus Noblelight GmbH. Kleinostheim, Germany.

The excimer lamp emits incoherent, pulsed ultraviolet radiation. Such radiation has a relatively narrow bandwidth, i.e., the half width is of the order of approximately 5 to 100 nanometers. Desirably, the radiation will have a half width of the order of approximately 5 to 50 nanometers, and more desirably will have a half width of the order of 5 to 25 nanometers. Most desirably, the half width will be of the order of approximately 5 to 15 nanometers.

The ultraviolet radiation emitted from an excimer lamp can be emitted in a plurality of wavelengths, wherein one or more of the wavelengths within the band are emitted at a maximum intensity. Accordingly, a plot of the wavelengths in the band against the intensity for each wavelength in the band produces a bell curve. The "half width" of the range of ultraviolet radiation emitted by an excimer lamp is defined as the width of the bell curve at 50% of the maximum height of the bell curve.

The emitted radiation of an excimer lamp is incoherent and pulsed, the frequency of the pulses being dependent upon the frequency of the alternating current power supply which typically is in the range of from about 20 to about 300 kHz. An excimer lamp typically is identified or referred to by the wavelength at which the maximum intensity of the radiation occurs, which convention is followed throughout this specification and the claims. Thus, in comparison with most other commercially useful sources of ultraviolet radiation which typically emit over the entire ultraviolet spectrum and even into the visible region, excimer lamp radiation is essentially monochromatic.

As a result of the arylketoalkene wavelength-specific sensitizer of the present invention absorbing radiation in the range of about 250 to about 350 nanometers, and more particularly at about 270 to 320 nanometers, the wavelength specific photoreactor composition of the present invention will generate one or more reactive species upon exposure to sunlight. According, this wavelength specific photoreactor composition of the present invention provides a method for the generation of reactive species that does not require the presence of a special light source. This wavelength specific photoreactor composition of the present invention having the arylketoalkene sensitizer enables the production of adhesive and coating compositions that consumers can apply to a desired object and polymerize or cure upon exposure to sunlight. This wavelength specific photoreactor composition also enables numerous industry applications wherein unsaturated polvmerizable materials may be polymerized merely upon exposure to sunlight. Therefore, depending upon how the wavelength specific photoreactor composition is designed, the wavelength specific photoreactor composition of the present invention having the arylketoalkene sensitizer can eliminate the cost of purchasing and maintaining light sources in numerous industries wherein such light sources are necessary without the wavelength specific photoreactor composition of the present invention.

The wavelength specific photoreactor compositions of the present invention also differ from the prior art in that the prior art sensitizers absorb a wide bandwidth of radiation. In fact, the prior art photoinitiators are designed to absorb as much radiation as possible over as wide a range as possible thereby increasing the efficiency of the photoinitiators when exposed to ordinary light. Whereas the sensitizer of the present invention absorbs a single wavelength of radiation. The use of a wavelength specific photoreactor composition capable of absorbing at a substantially single wavelength of radiation results in an extremely efficient photoreactor upon exposure to a very narrow bandwidth of radiation or upon exposure to a single wavelength of radiation.

As shown in the Examples below, the superiority of the wavelength specific photoreactor compositions of the present invention over known photoinitiators is clear, even when the radiation is not the essentially monochromatic emission. The effective tuning of the wavelength specific photoreactor composition for a specific wavelength band permits the wavelength specific photoreactor composition to more efficiently utilize the target radiation in the emission spectrum of the radiating source corresponding to the "tuned" wavelength band, even though the intensity of such radiation may be much lower than, for example, radiation from a narrow band emitter, such as an excimer lamp. In other words, the effectiveness of the wavelength specific photoreactor composition of the present invention is not necessarily dependent upon the availability or use of a narrow wavelength band radiation source.

Also, as shown in Example 4, the single-photoinitiator photoreactor of the present invention is exceptionally efficient. In Example 4, a mixture of GENOMER.RTM. 1500B with a concentration of only about 0.5% of the single-photoinitiator photoreactor produced in Example 3 is totally cured upon exposure to the excimer lamp. The concentration of wavelength specific photoreactor composition used in Example 4 is substantially lower than the amounts normally used in the prior art. Typical concentrations of conventional photoreactors or photoinitiators in the prior art are between approximately 2% to 20% by weight.

Further, as shown in Example 7, the multi-photoinitiator photoreactors of the present invention are even more efficient than the single-photoinitiator photoreactors of the present invention. More particularly, Table 2 summarizes the curing times for a pigmented polymerizable formulation, wherein either a commercial photoinitiator product, the wavelength specific photoreactor composition produced in Example 3 or the wavelength specific photoreactor composition produced in Example 6 is admixed therein. The wavelength specific photoreactor composition produced in Example 6 had the shortest curing time, namely, 0.06 seconds. The wavelength specific photoreactor composition produced in Example 3 had a curing time of 0.10, and the commercial photoinitiator had a cure time that is 50 times greater than the wavelength specific photoreactor composition of Example 6, namely 3.0 seconds.

Accordingly, a major advantage of the wavelength specific photoreactor compositions of the present invention is that they have rapid curing times in comparison to the curing times of the prior art. Another advantage of the of the present invention is that the multi-photoinitiator photoreactors of the present invention have even faster curing times in comparison to the single-photoinitiator photoreactors of the present invention. Yet another advantage of the present invention is that the multi-sensitizer photoreactors and the multi-photoinitiator photoreactors of the present invention are highly sensitive photoreactors and are beneficially used in situations having lower light levels.

The present invention is further described by the examples which follow. Such examples, however, are not to be construed as limiting in any way either the spirit or the scope of the present invention. In the examples, all parts are by weight, unless stated otherwise.

EXAMPLE 1

This example describes a method of synthesizing the following wavelength-specific sensitizer: ##STR17##

The wavelength-specific sensitizer is produced as summarized below: ##STR18##

To a 250 ml round bottom flask fitted with a magnetic stir bar, and a condenser, is added 10.8 g (0.27 mole) sodium hydroxide (Aldrich), 98 g water and 50 g ethanol. The solution is stirred while being cooled to room temperature in an ice bath. To the stirred solution is added 25.8 g (0.21 mole) acetophenone (Aldrich) and then 32.2 g (0.21 mole) 4-carboxybenzaldehyde (Aldrich). The reaction mixture is stirred at room temperature for approximately 8 hours. The reaction mixture temperature is checked in order to prevent it from exceeding 30.degree. C. Next, dilute HCl is added to bring the mixture to neutral pH as indicated by universal pH indicator paper. The white/yellow precipitate is filtered using a Buchner funnel to yield 40.0 g (75%) after drying on a rotary pump for four hours. The product is used below without further purification.

The resulting reaction product had the following physical parameters:

Mass. Spec. m/e (m.sup.+) 252, 207, 179, 157, 105, 77, 51.

The ultraviolet radiation spectrum of the product had an extinction coefficient of about 24,000 at about 304 nanometers, and .lambda..sub.max is at 308 nanometers.

EXAMPLE 2

This example describes a method of making the following wavelength-selective sensitizer, namely 4-[4'-carboxy phenyl]-3-buten-2-one: ##STR19##

The wavelength-specific sensitizer is produced as summarized below: ##STR20##

The method of Example 1 is followed except that acetone (Fisher, Optima Grade) is added first, and then the carboxybenzaldehyde is added. More particularly, 32.2 g (0.21 mole) of carboxybenzaldehyde is reacted with 12.2 g (0.21 mole) of acetone in the sodium hydroxide/ethanol/water mixture described in Example 1. Dilute HCl is added to bring the reaction mixture to neutral pH, yielding 37.1 g (91%) of a pale yellow powder which is used without further purification in the following examples.

The resulting reaction product, namely 4-[4'-carboxy phenyl]-3-buten-2-one, had the following physical parameters:

Mass. Spec. 190 (m.sup.+), 175, 120.

EXAMPLE 3

This example describes a method of covalently bonding the compound produced in Example 2 to a photoinitiator, namely IRGACURE.RTM. 2959 (1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one or 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone), as is summarized below: ##STR21##

To a 500 ml round bottom flask fitted with a magnetic stir bar, and condenser, is placed 20 g (0.08 mole) of the composition prepared in Example 28, 17.8 g (0.08 mole) IRGACURE.RTM. 2959 (Ciba-Geigy, N.Y.), 0.5 g p-toluenesulfonic acid (Aldrich), and 300 ml anhydrous benzene (Aldrich). The Dean and Stark adapter is put on the flask and the reaction mixture heated at reflux for 8 hours after which point 1.5 ml of water had been collected (theo. 1.43 ml). The reaction mixture is then cooled and the solvent removed on a rotary evaporator to yield 35.4 g. The crude product is recrystallized from 30% ethyl acetate in hexane to yield 34.2 g (94%) of a white powder. The resulting reaction product had the following physical parameters:

Mass. Spectrum: 458 (m.sup.+), 440, 399, 322, 284.

EXAMPLE 4

The following experiment tested the curing ability of the compound produced in Example 3. More particularly, the compound produced in Example 3 is mixed with the difunctional alkyl urethane acrylate adhesive GENOMER.RTM. 1500B (Mader, Biddle Sawyer Corporation, New York. N.Y.) and exposed to 308 nm excimer lamp on a conveyor belt. Two formulations are studied:

Formulation I

About 0.05 g of the compound produced in Example 3 is mixed with 10 g of GENOMER.RTM. 1500B. Therefore the concentration of the compound produced in Example 3 in the mixture is about 0.5%. These components are mixed by means of a magnetic stirring bar at 80.degree. C. A few drops of the mixture is placed on a heated metal plate (Q-Panel Company, Westlake, Ohio) and drawn down to a thickness of about 0.1 mm by means of a 0 draw-down bar (Industry Tech., Oldsmar, Fla.).

Formulation II

About 0.025 g of IRGACURE.RTM. 2959 is mixed with 10 g of GENOMER.RTM. 1500B. These components are mixed and then drawn out on heated metal plates with a 0 draw-down bar as per Formulation I.

Each plate is then exposed to a 308 nanometer excimer lamp on a conveyor belt for approximately 0.8 seconds. The conveyor belt is set at 50 feet/minute. The plate having Formulation I thereon is totally cured upon exposure to the excimer lamp. In contrast, the plate having Formulation II thereon remained tacky and is not fully cured.

EXAMPLE 5

This example describes the evaluation of the curing behavior of an adhesive containing the wavelength specific photoreactor compositions of Example 3 as reported in Example 4 upon exposure to ultraviolet radiation from an excimer lamp.

An excimer lamp configured substantially as described by Kozelschatz and Eliasson et al., supra. is employed and is shown diagrammatically in FIG. 1. With reference to FIG. 1, the excimer lamp 100 consisted of three coaxial quartz cylinders and two coaxial electrodes. The outer coaxial quartz cylinder 102 is fused at the ends thereof to a central coaxial quartz cylinder 104 to form an annular discharge space 106. An excimer-forming gas mixture is enclosed in the annular discharge space 106. An to inner coaxial quartz cylinder 108 is placed within the central cylinder 104. The inner coaxial electrode 110 consisted of a wire wound around the inner cylinder 108. The outer coaxial electrode 112 consisted of a wire mesh having a plurality of openings 114. The inner coaxial electrode 110 and outer coaxial electrode 112 are connected to a high voltage generator 116. Electrical discharge is maintained by applying an alternating high voltage to the coaxial electrodes 110 and 112. The operating frequency is 40 kHz, the operating voltage 10 kV. Cooling water is passed through the inner coaxial quartz cylinder 108, thereby maintaining the temperature at the outer surface of the lamp at less than about 120.degree. C. The resulting ultraviolet radiation is emitted through the openings 114 as shown by lines 118. The lamp is used as an assembly of four lamps 100 mounted side-by-side in a parallel arrangement.

A film of adhesive is deemed cured completely, i.e., through the entire thickness of the film, when it passed the scratch test; see, e.g., M. Braithwaite et al., "Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints," Vol. IV, SITA Technology Ltd., London, 1991, pp. 11-12.

EXAMPLE 6

This example describes a method of covalently bonding two photoinitiators, namely IRGACURE.RTM. 2959, to a chalcone sensitizer of the present invention, as is summarized below in a two step reaction: ##STR22## Step A

To a 250 ml round bottom flask fitted with a magnetic stir bar is added 5.4 g sodium hydroxide (Aldrich), 5 ml water, and 45 ml ethanol, and the solution is cooled in a water bath. When the reaction mixture is at room temperature, 15.7 g (0.10 mole) carboxybenzaldehyde (Aldrich), and 17.2 g (0.10 mole) acetylbenzoic acid (Aldrich) are added and the solution stirred overnight (12 hours). The reaction mixture is then chilled in an ice bath and the solution neutralized/acidified with dilute HCl until pH indicator paper showed a pH of 3 to 5. The yellow precipitate is filtered and the solid is dried overnight in a vacuum desiccator. The product of this reaction is the di-carboxylic acid substituted chalcone illustrated above. The yield is 28.1 grams (90%).

Step B

In a 500 ml round bottom flask flushed out by argon is placed a magnetic stir bar, 23.6 g (0.08 mole) of the di-carboxylic acid substituted chalcone produced above in step A, 200 ml of dry dichloromethane (Aldrich), 35.6 g (0.16 mole) IRGACURE.RTM. 2959 (Ciba-Geigy), and 0.8 g dimethylaminopyridine (Aldrich). The reaction mixture is cooled in an ice bath to 0.degree. C., and then 18.4 g of DCC (Aldrich) is added over 5 minutes and the solution is allowed to warm to room temperature, and is stirred overnight. The reaction mixture is filtered and washed with 0.5 N HCl aqueous followed by saturated NaHCO.sub.3 solution. The organic layer is separated, dried (Na.sub.2 SO.sub.4) and the solvent removed under reduced pressure to yield a pale yellow solid. The product is the multi-photoinitiator photoreactor illustrated above. The yield is 51.8 g (91%).

The resultant reaction product had the following physical parameters:

.sup.1 H NMR [CDCL.sub.3 ] .delta. 1.7 [s], 4.0 [d], 4.2 [d], 7.0 [d], 7.2-8.2 [nu].

Note that the ratio of CH.sub.3 to CH.dbd.CH is 12 to 2, thus indicating that there are two IRGACURE.RTM. 2959 to one mole of chalcone.

EXAMPLE 7

The following experiment tested the curing ability of the wavelength specific photoreactor composition produced in Example 6 in comparison to the wavelength specific photoreactor composition produced in Example 3 and to a commercially available photoinitiator product. More particularly, the same formulation to be cured is mixed with a commercial initiator product (3.5% IRGACURE.RTM. 907 with 3.5% ITX coinitiator, by weight), or with the wavelength specific photoreactor composition produced in Example 3, or with the wavelength specific photoreactor composition produced in Example 6. Each mixture is drawn into a 50 micron film and then cured. The formulation is an offset press formulation of a high molecular weight urethane acrylate having a molecular weight of above 100,000. Also, as the formulation is thixotropic, the formulation also contains approximately 5% clay.

More specifically, approximately 2 grams of the formulation for offset presses is placed in an aluminum pan and the corresponding weight of the appropriate photoinitiator then added to give a 6 to 7% concentration by weight of the photoinitiator. Table 2 reports the concentrations of each of the photoreactors in their respective formulation mixtures. The mixture is heated on a hot plate set at a low heat and the mixture stirred for five minutes to ensure mixing. A small amount of the mixture is then placed on a Q-Panel (3 inch by 5 inch) plate and drawn down to a film thickness of 50 microns using an `O` or "3" bar. The plate is then placed under a 308 nm excimer lamp and exposed the light until the mixture is cured, as determined by the scratch and twist test. The excimer lamp has an input power of approximately 2.5 kilowatts, and an output power of approximately 0.1 watt per square centimeter per lamp bulb.

Table 1 summarizes the curing times for the clear coating. As shown below, the wavelength specific photoreactor compositions of the present invention, as produced in Examples 3 and 6, had cure times of only 0.04 seconds, wherein the commercial photoinitiator had a cure time that is 40 times greater, namely, 1.6 seconds.

                  TABLE 1
    ______________________________________
    Cured Offset Press
    Coatings*         Cure Time
    (50 micron film)  (Sec)
    ______________________________________
    Clear Coating     1.6
    (Commercial Initiator)
    Clear Coating     0.04
    (Example 3 Photoreactor)
    Clear Coating     0.04
    (Example 6 Photoreactor)
    ______________________________________
     *Paste formulations which contain a clay agent to introduce thixotropic
     properties

Table 2 summarizes the curing times for a pigmented coating, wherein the formulation described above is further admixed with 15% by weight of a green pigment, namely, Gamma Cure. As shown below, the wavelength specific photoreactor composition produced in Example 6 had the shortest curing time, namely, 0.06 seconds. The wavelength specific photoreactor composition produced in Example 3 had a curing time of 0.10, and the commercial photoinitiator had a cure time that is 50 times greater than the wavelength specific photoreactor composition of Example 6, namely 3.0 seconds.

                  TABLE 2
    ______________________________________
    Cured Offset Press
    Coatings*         Cure Time
                               Conc. of
    (50 micron film)  (Seconds)
                               Photoreactor
    ______________________________________
    Clear Coating     3.0      7%
    (Commercial Initiator)
    Clear Coating     0.10     6%
    (Example 3 Photoreactor)
    Clear Coating     0.06     6%
    (Example 6 Photoreactor)
    ______________________________________
     *Paste formulations which contain a clay agent to introduce thixotropic
     properties

EXAMPLE 8

The following experiment tested the curing ability of the wavelength specific photoreactor composition produced in Example 6 in comparison to the wavelength specific photoreactor composition produced in Example 3 and to a commercially available photoinitiator product, wherein the power setting for the excimer lamp is varied. With the exception of varying the power setting of the excimer lamp, all other aspects of the experiment are described in Example 7. Table 3 summarizes the curing times for the clear and pigmented formulations, wherein "full" represents full lamp power, "0.75" represents 75% lamp power, etc.

                  TABLE 3
    ______________________________________
                Excimer Lamp Power Setting
    Sample        Full   0.75       0.50 0.25
    ______________________________________
    Commercial
    Initiator 7%
    Clear         1.6    2.0        2.5  4.0
    Pigmented     3.0    5.0        7.5  15.0
    Example 3
    Photoreactor 6%
    Clear         0.04   0.08       0.10 0.26
    Pigmented     0.10   0.14       0.22 0.34
    Example 6
    Photoreactor 6%
    Clear         0.04   0.06       0.12 0.16
    Pigmented     0.04   0.08       0.18 0.20
    ______________________________________

EXAMPLE 9

Examples 9 through 12 describe the synthesis of the wavelength specific photoreactor composition shown as the reaction product in Example 12.

In a 1 liter 3-necked round bottomed flask fitted with a mechanical stirrer and condenser, is placed 200 g (1.56 moles) of cyclohexyl carboxylic acid (Aldrich) and 223 g (1.2 eq) of thionyl chloride (Aldrich). The reaction mixture is stirred and heated to reflux. 50 ml of toluene is added to allow the reaction mixture to become a solution. After 1 hour, 300 ml of dry toluene is added and the solvent is distilled off. 200 ml of toluene with a small amount of thionyl chloride is distilled off and the distillate has a steady boiling point of approximately 110.degree. C. The condenser is then mounted back for reflux and 300 ml of dry toluene is added along with 141 g (1.5 moles) of phenol (Aldrich) and the mixture is refluxed for 12 hours. The solvent is then removed under reduced pressure to leave a pale brown oil. The yield is 287 g (94%). ##STR23##

The resulting reaction product had the following physical parameters:

.sup.1 H NMR [CDCl.sub.3 ] .delta. 1.2-2.8 (m), 1.8 (m), 2.0(m), 6.9-7.5 (m), ppm.

HPLC 90% Ch.sub.3 CN/10% H.sub.2 O--C.sub.18 Column: Retention time of 5.8 minutes

EXAMPLE 10

To a 1 liter 3-necked round bottom flask fitted with a mechanical stirrer, condenser and flushed with argon, is added 65.2 a of aluminum chloride (Aldrich), 100 ml of carbon disulfide (Aldrich). To this stirred suspension is slowly added 100 g (0.69 moles) of the ester from Example 9, and the mixture is stirred under reflux overnight (12 hours). The mixture is then a thick brown sludge which is broken up by the addition of dilute HCl. The reaction mixture is poured into a separatory funnel and extracted three times with 150 ml each of ether. The ether extracts are combined, washed with ice cold water, dried over MgSO.sub.4 and the ether is removed to give 95 g (95% yield) of a thick light brown oil. ##STR24##

The resulting reaction product had the following physical parameters:

.sup.1 H NMR [CDCl.sub.3 ] .delta. 0.8-2.3 (m), 3.7 (s), 2.0(m), 7.2-7.7 (m), ppm.

EXAMPLE 11

In a 1 liter, 3 necked round bottomed flask fitted with a mechanical stirrer and a condenser, an inlet gas tube and a bubbler fitted to the condenser, is placed 90 g (0.44 moles) of the ketophenol from Example 10, and 300 ml of dry tetrahydrofuran. The reaction mixture is chilled in a salt/ice bath and 98.5 g (0.88 moles) of potassium t-butoxide is added. After 20 minutes, a stream of dry oxygen is bubbled into the reaction mixture for 2 hours. The reaction mixture is then neutralized with dilute HCl and then extracted three times each with 100 ml of ether. The combined extracts are then washed with water, dried over MgSO.sub.4 and the solvent removed under reduced pressure to yield 95.2 g of a thick oil (98% yield). ##STR25##

The resulting reaction product had the following physical parameters:

.sup.1 H NMR [CDCl.sub.3 ] .delta. 0.8-2.3 (m), 3.7 (s), 2.0(m), 4.6 (s), 7.2-7.7 (7m), ppm.

EXAMPLE 12

In a 1 liter, 3-necked round bottomed flask fitted with a mechanical stirrer and a condenser is placed 50 g (0.2 moles of the product from Example 6 and 23.6 g (0.2 moles) of thionyl chloride and 50 mls of dry toluene. The reaction mixture is heated to reflux for 2 hours after which the condenser is turned to allow distillation of the toluene and any unreacted thionyl chloride. An additional 150 ml of toluene is added and 100 ml allow-ed to be distilled giving a steady 110.degree. C. boiling point. 200 ml of fresh, dry toluene is added and the condenser adjusted to its reflux position. ##STR26##

To the reaction mixture is slowly added 44 g (0.2 moles) of the diol from Example 11 and the mixture is allowed to reflux for 12 hours. The solution is then removed under reduced pressure to yield 86.7 g (95% yield) of a light yellow solid. The solid is recrystalized from benzene to yield a yellow crystalline material with a melting point of 127-128.degree. C. ##STR27##

EXAMPLE 13

Examples 13 through 17 describe the synthesis of the double-wavelength specific sensitizer photoreactor shown as the product in Example 17.

In a 500 ml round bottomed flask fitted with a magnetic stirrer and a condenser is placed 122.1 g of sodium hydroxide, 100 ml of water, and 100 ml of ethanol. The solution is stirred and 125 g (0.73 mole) of ethyl 4-hydroxycyclohexane carboxylate is added. The solution refluxed for 2 hours, cooled and the solution is neutralized with dilute HCl. The solution is then extracted three times with 100 ml of ether (3.times.100 ml). The ether is separated, dried (MgSO.sub.4) and removed under reduced pressure to yield 100 g of a white powder. (95.1 % yield) ##STR28##

The resulting reaction product had the following physical parameters:

.sup.1 H NMR [CDCl.sub.3 ] .delta. 1.5-1.7 (m), 1.8 (m), 2.0(m), 3.8 (m), 4.8-5.0 (m) ppm.

EXAMPLE 14

To a 3 necked round bottom flask (500 ml) fitted with a mechanical stirrer and a condenser, is placed 90 g (0.62 moles) of 4-hydroxycyclohexyl carboxylic acid and 89.2 g of thionyl chloride, and the mixture is stirred for one hour before heating to reflux. On reflux, 80 ml of dry toluene is added and the mixture stirred for an additional hour. 100 ml of toluene is added and the liquid distilled to remove any excess thionyl chloride. After 50 ml is distilled, another 50 ml of toluene is added, and the distillation continued until 120 ml of toluene/thionyl chloride is collected. ##STR29##

The distillation is stopped and the condenser is fitted for reflux. To the mixture is added 100 ml of toluene and 58.3 g (0.62 moles) of phenol and the reaction mixture refluxed for 12 hours. The solvent is then removed under reduced pressure to yield 113 g (83%) of a light yellow oil. ##STR30##

The resulting reaction product had the following physical parameters:

.sup.1 H NMR [CDCl.sub.3 ]1.6-3.0 (m), 6.8-7.5 (m) ppm

EXAMPLE 15

To a 3 necked 500 ml round bottom flask fitted with a mechanical stirrer and a condenser, is placed 60.4 g (0.45 moles) anhydrous aluminum chloride and 100 ml of carbon disulfide. To this mixture is slowly added 100 g (0.45 moles) of the ester from Example 14. The mixture is stirred for one hour and then heated to reflux for eight hours. The reaction is cooled and dilute HCl is added slowly and the mixture stirred for two hours. The reaction mixture is poured into a separatory funnel and extracted three times with 100 ml with ether. The organic layer is then removed to yield an oil (95 g, 86% yield). ##STR31##

The resulting reaction product had the following physical parameters:

.sup.1 H NMR [CDCl.sub.3 ] .delta. 1-3 (m), 6.8-7.6 (m), ppm.

EXAMPLE 16

In a 500 ml round bottom flask fitted with a mechanical stirrer and a condenser and being flushed with dry argon is placed 137.8 g (1.23 moles) potassium t-butoxide, 200 ml of dry tetrahydrofuran and the solution chilled in a salt-ice bath. 90 g (0.41 moles) is added and the solution stirred for 30 minutes. Dry air is then bubbled into the solution for 2 hours. The solution is quenched with 50 ml water and neutralized with dilute HCl. The reaction mixture is extracted with ether (3.times.100 ml), and the ether and solvents removed to yield 90.1 g (93% yield) of the triol. ##STR32##

The resulting reaction product had the following physical parameters:

.sup.1 H NMR [CDCl.sub.3 ] .delta. 1-3 (m), 6.8-7.6 (m), ppm.

EXAMPLE 17

To a solution of 183.8 g (0.78 moles) of the acid chloride from Example 12 in 300 ml of toluene in a 2 liter 3-necked flask fitted with a condenser and mechanical stirrer, is added 80.0 g (0.36 moles) of the triol and the solution is refluxed for 8 hours. Removal of the toluene gave a light yellow powder which is recrystallized from benzene to yield 201.1 g (84%) of pale yellow crystals. ##STR33##

The resulting reaction product had the following physical parameters:

.sup.1 H NMR [CDCl.sub.3 ] .delta. 1.5-2.8 (m), 7.6-9.7 (m), ppm.

EXAMPLE 18

The cure rate of off-set press black ink is checked using the new compound from Example 17 under an excimer lamp (308 nm radiation).

1. A 5% wt/wt mixture of 14% black pigmented off-set press ink is made with the compound from Example 17 in an aluminum pan and heated to ensure good mixing. The black ink is drawn out on a hot (60.degree. C.) plate using a zero-draw-down bar to give a film of 20-30 micron thickness. The film is exposed to 0.1 seconds flash of 308 nm excimer lamp radiation and the degree of cure determined by scratch and twist analysis.

The thinner parts of the film had a total cure, and the thicker parts had a skin cure.

2. A 2.5% wt/wt ink is made as previously described and drawn down with the zero draw-down bar. The ink is exposed to 0.1 seconds of 308 nm radiation resulting in a complete cure of the film.

Using a higher concentration (5%) of the compound from Example 17, apparently is too high a concentration and the double antenna system shields the layer before and gives slower curing. It is believed that the antenna system shields the layers below and gives slow curing.

While the specification has been described in detail with respect to specific embodiments thereof, it will be appreciated that those skilled in the art, upon attaining an understanding of the foregoing, may readily conceive of alterations to, variations of, and equivalents to these embodiments. Accordingly, the scope of the present invention should be assessed as that of the appended claims and any equivalents thereto.

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Current U.S. Class:	522/34; 428/378; 442/59; 442/152; 442/164; 442/172; 522/33; 522/36; 522/39; 522/40; 522/42; 522/71; 522/81
Intern'l Class:	C08F 002/50; C08J 003/28
Field of Search:	522/8,9,14,16,19,34,36,39,42,40,71,81 428/378 442/59,152,164,172